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Carbonyls as free-radical precursors

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Carbonyls as free-radical precursors cyclizations of unsaturated and epoxy carbonyls
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Kinter, Kevin S
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vii, 105 leaves : ill. ; 29 cm.

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Alkenes ( jstor )
Chromatography ( jstor )
Electrons ( jstor )
Epoxy compounds ( jstor )
Flasks ( jstor )
Free radicals ( jstor )
Hydrogen ( jstor )
Ketones ( jstor )
Tetrahedrons ( jstor )
Tin ( jstor )
Chemistry thesis Ph. D
Cyclic compounds ( lcsh )
Dissertations, Academic -- Chemistry -- UF
Free radicals (Chemistry) ( lcsh )
Ketones ( lcsh )
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bibliography ( marcgt )
non-fiction ( marcgt )

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Thesis:
Thesis (Ph. D.)--University of Florida, 1993.
Bibliography:
Includes bibliographical references (leaves 98-103).
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Typescript.
General Note:
Vita.
Statement of Responsibility:
by Kevin S. Kinter.

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CARBONYLS AS FREE-RADICAL PRECURSORS:
CYCLIZATIONS OF UNSATURATED AND EPOXY CARBONYLS















BY


KEVIN S. KINTER


A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY



UNIVERSITY OF FLORIDA


1993




CARBONYLS AS FREE-RADICAL PRECURSORS:
CYCLIZATIONS OF UNSATURATED AND EPOXY CARBONYLS
BY
KEVIN S. KINTER
A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
1993


To Mom and Dad
with all my love and appreciation


ACKNOWLEDGEMENTS
The only words that I think aptly describe the last 10
years of my life are from Jerry Garcia, "What a long, strange
trip it's been." I can only hope that there is life after
education. It seems like it was just yesterday that I was
leaving home for the first time to go to a strange place
called college. I cannot even begin to comprehend all of the
things that have happened to me since that day. But there
are many people who I can thank for all their help, guidance,
understanding, and friendship.
First and foremost, I would like to thank my research
director, Dr. Eric Enholm, for all of his patience, guidance,
and assistance. His help in the preparation of this
manuscript was immeasurable. I would also like to thank my
undergraduate research director, Dr. Gary Crowther, for
introducing me to the wonderful world of chemistry. I would
like to thank all of the professors in the division of
organic chemistry who showed me that there were many facets
to being a Ph.D. chemist. I would also like to thank Dr.
Girija Prasad for training me and for his contributions to
the unsaturated ketone project.
The thing that I will remember best and miss most about
the University of Florida is the many friendships that I have
in


developed since I have been here. Thanks go to Keith Palmer
and Brent Kleintop for putting up with me this long and for
showing me the mechanistic side of organic chemistry (Keith)
and that analytic chemists are not just mechanics (Brent).
Thanks also go to fellow graduate students and fantasy
football friends Don Eades and Larry Villanueva for many
drunken hours of Gator sports prognosticating. Additional
thanks are extended to all of the past and present members of
the Enholm research group, especially Janet Burroff, Hikmet
Satici, and Jeff Schreier. I wish them all the best of luck
in their careers and personal lives.
I am also grateful to Karin Larsen for making this last
year very pleasant, despite the problems encountered at work.
I wish that we had met earlier, but I hope we will continue
to build on what we have begun. My family truly deserves the
most appreciation though. Thanks go to my oldest brother,
Mike, who showed that a Kinter could get his Ph.D., and to
Chris for being an organic comrade in the family. Thanks go
also to Jim and Tom for showing me that there is more to life
than chemistry. But most of all, I am truly indebted to my
parents. Without the emotional and financial support of my
parents I would never have been able to achieve this goal. I
feel very fortunate to have had these opportunities, which
would not have been possible without the support of all of
those persons mentioned above. For this I will always be
indebted to them.
IV


TABLE OF CONTENTS
ACKNOWLEDGEMENTS iii
ABSTRACT vi
CHAPTERS
1 INTRODUCTION 1
2 CYCLIZATIONS OF Cl,(3-UNSATURATED KETONES 28
3 CYCLIZATIONS OF a,(3-EPOXY CARBONYLS 48
4 SUMMARY 71
5 EXPERIMENTAL 75
General 75
Experimental Procedures and Results 7 6
LIST OF REFERENCES 98
BIOGRAPHICAL SKETCH 104
V


Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy
CARBONYLS AS FREE-RADICAL PRECURSORS:
CYCLIZATIONS OF UNSATURATED AND EPOXY CARBONYLS
By
Kevin S. Kinter
May, 1993
Chairman: Eric J. Enholm
Major Department: Chemistry
This dissertation investigated the tributyltin hydride
induced cyclization reactions of unsaturated ketones and
epoxy carbonyls with olefins. The reaction of tributyltin
hydride with aldehydes and ketones produces an O-stannyl
ketyl, which has both anionic and radical character. The
goal of this study was to ascertain whether the radical
reactivity of the O-stannyl ketyl could be delocalized away
from the central-carbon atom by the participation of labile
functional groups.
The first area of study was the intramolecular coupling
of unsaturated ketones with alkenes to produce functionalized
cyclopentanes. Unactivated alkenes were found to be
unsuitable as radical acceptors and activation of the alkene
was essential to the cyclization. A dilution study revealed
vi


that excellent anti stereoselectivities (>50:1) could be
achieved, and this was attributed to a reversible
cyclization. Product identification and enolate trapping
studies demonstrated that the anionic character of the tin
ketyl could also be utilized. This was the first reagent-
based approach to study the coupling of the (3-carbons of
these systems.
The second area of study investigated the cyclizations
of epoxy carbonyls with olefins. The C-0 bond of the epoxide
was fragmented by the adjacent tin ketyl radical to produce
an alkoxy radical. This project was originally designed to
produce tetrahydrofurans, however these reactions produced
functionalized cyclopentanols. Originally it was believed
that the reactions were proceeding through a hydrogen
abstraction mechanism, but after further experimentation a
rare 1,5-tin transfer mechanism was proposed.
Vll


CHAPTER 1
INTRODUCTION
The term "free radical" applies to a species which
possesses one unpaired electron.1 Free radicals were once
thought to be indiscriminate, highly reactive intermediates,
but lately are being viewed in a kinder, gentler light.2
Radicals are formed by a homolytic cleavage of a covalent
bond. The central atom is usually sp2 hybridized and the
unpaired electron rests in the p-orbital.3 The reactivity
which radicals exhibit is dominated firstly by the nature of
the central atom and secondly by the substituents which are
attached to it.2
Free radicals have been known since 1900 when Gomberg
investigated the formation and reactions of triphenylmethyl
radical.4'5 Paneth not only discovered that less stable alkyl
radicals exist, but also measured their lifetimes in the gas
phase.6 Synthetic applications of radicals began in 1937
when Hey and Waters described the phenylation of aromatic
compounds by dibenzoyl peroxide.7 In the same year Kharasch
proposed that the anti-Markovnikov addition of hydrogen
bromide to an alkene was also a radical chain process.8
Until the 1970s, synthetic free radical chemistry developed
1


2
slowly and was mostly applied only to copolymerization
reactions 9'10
In the 1970s though, new synthetic methods involving
free radicals began to be developed,11'12 and lately radical
cyclizations have become integral parts of many elegant
syntheses.13 The power and versatility of radical chemistry
is best demonstrated by Dennis Curran's synthetic work
towards the class of natural products known as triquinanes.14
Curran and Rakiewicz's landmark synthesis of hirsutene 2., as
shown in Scheme 1-1,15 utilizes a tandem radical cyclization
approach as the key step. The linear triquinane was produced
in a single step by a tandem sequence commencing with the
TBTH,AIBN
c6h6,A
H H
1 2
Scheme 1-1
generation of a 5-hexenyl radical from primary iodide X which
was captured by the olefin and finally terminated by addition
to the suitably disposed alkyne. Curran has also used tandem
radical cyclizations in the synthesis of other members in the
triquinane family (Figure 1-1), such as capne1lene, 1 6
coriolin, 17 modhephene X, 18 silphiperf olene , 19 and
17
hypnophilin


3
Figure 1-1
Other triquinanes synthesized by Curran
Before one can appreciate the complexity and grace of
the aforementioned syntheses one must understand the basic
principles of these reactions. Radical processes typically
are chain reactions, and the first element of a chain
reaction is initiation. Many reagents which will begin a
radical chain reaction are available to the synthetic
chemist.2 The reagent of choice, from both a safety and a
practical standpoint, is azobisisobutyronitrile (AIBN) H,
which is thermally decomposed to give cyanoisopropyl radicals
(Scheme 1-2) These radicals are not reactive enough to
abstract alkyl's hydrogens, but they are capable of
abstracting a hydrogen atom from the weak Sn-H bond of
tributyltin hydride (TBTH) to produce the very useful
tributyltin radical H.2
For more than 20 years tributyltin hydride has been
known to engage in free radical reactions.20 The chemistry
that TBTH engages in is too extensive to cover here, but good


4
reviews of its reactions are available.1'13'21'22'23 It is
commercially available and it can be prepared from
bistributyltin oxide and polymethylhydoxy siloxane.24 Lately,
there have also been some tin hydride reagents developed
which are immobilized on polystyrene beads.25 Although there
are many different initiators and reagents, this discussion
will focus mainly on the AIBN/TBTH system which was employed
in my work. The majority of current radical reactions are
based on the chemistry of this reagent combination.22
Scheme 1-2
For a chain reaction to develop, the radicals formed in
the initiation steps must propagate. Propagation (Scheme 1-
3) occurs when a radical JJL. interacts with a nonradical L2 to
produce a new radical species JL2.. Without propagation the
chain would never develop because if two radicals combine to
form a nonradical, the process is terminated. Careful
control of reaction variables, such as concentration and the


5
substrate to initiator ratio, helps to avoid such
nonproductive reactions. The organotin radical which is
produced is not synthetically useful until it reacts with
other functional groups to generate an organic-centered
radical.
Bu3Sn + R-X
R- + Bu3Sn-X (3)
11
Bu3Sn
11
+
12 13 14
X= Halogen, -SR', -SeR', -N02
Bu3
15 16
(4)
x= c, o, s
Scheme 1-3
There are two broad classes of free radical reactions:
atom or group abstraction (eq. 3) and addition to multiple
bonds (eq. 4 and 5) Halide abstraction was discovered in
1957,26 and has achieved great importance in organic
chemistry since. Atom abstraction involves an Sh2 reaction
by tin radical to generate an organic radical. Bromine and
iodine are most commonly used because chlorine reacts
sluggishly and fluorine is unreactive. The degree of


6
substitution of the carbon which bears the halide also has an
effect on the rate of this reaction, which is as follows:
1 RX < 2RX < 3RX.27 This trend parallels the relative
stability of the resultant alkyl radicals.
Thiols and thioethers can also be reduced cleanly with
TBTH, due to the strong tin-sulfur bond which is formed.21
Thioketals can also be reduced in the same manner, which
offers an interesting alternative for ketone reduction.28 The
most useful of the sulfur-related reductions involves the
addition, fragmentation reactions of thiocarbonyls which were
developed by Barton and McCombie.29 This deoxygenation
methodology was developed because of the inactivity of
alcohols towards TBTH reductions. This method can be applied
to a large variety of hydroxy compounds, including primary,
secondary, tertiary, and diols.21 It has been used in the
synthesis of many natural products such as compactin,30
anguidine,31 and gibberellin.32
Another way in which tin can generate a carbon-centered
radical is by its addition to multiple bonds. When JL1 adds
to alkenes or alkynes the ensuing radical JJL or _L8_ can then
abstract a hydrogen from TBTH, giving the hydrostannated
products JJL and -2-Q-. In the process another molecule of
tributyltin radical, which satisfies the last criterion for a
radical chain reaction, has been generated. When a terminal
alkyne is reacted, the tributyltin will add to the terminus.
The reaction proceeds through overall anti-addition, which
gives the Z olefin as the kinetic product, but excess tin can


7
equilibrate the reaction mixture so that the
thermodynamically favored E-olefin is produced.21
Scheme 1-4
The chemistry which is most important to this thesis is
how tin reacts with carbonyls. Researchers have postulated
that the hydrostannation of a ketone or aldehyde carbonyl can
occur by two different mechanisms, depending on the reaction
conditions, shown in Scheme 1-5.21 When polar solvents and
Lewis acid catalyst are utilized the ionic pathway dominates
(eq. 6) In this mechanism, TBTH acts as a true "hydride
donor" giving intermediate 22. which reorganizes to give the
tin alkoxide. An alcohol can be obtained when 23 is treated
either with proton sources or with additional TBTH.21 Silica
gel33 and tributyltin triflate34 have proved to be valuable
catalysts.
An alternative mechanism is the way in which TBTH reacts
with carbonyls through a free radical pathway (eq. 7) The
formation of the O-stannyl ketyl 2_4_ in this case arises from


8
O
21
Lewis
Acid
+ H-SnBu3 *
Polar
Solvent
9
22
OSnBu3
H
23
A-
OSnBu3
SnBui
AIBN
C6H6,A
TBTH
OSnBu3
+ Bu3Sn (7)
21
24
H
23
11
Scheme 1-5
the tributyltin radical reacting at the oxygen of the
carbonyl to form a carbon-centered radical. This radical
then abstracts a hydrogen atom to produce the tin alkoxide
species 2_3_, and the tributyltin radical can now repeat the
process. It is this second type of reactivity, radical
addition to carbonyls, which will be the principal focus of
this dissertation.
Historically, rarely studied O-stannyl ketyls were first
described by Tanner et al.,35 and later by both Beckwith and
Roberts36 and Sugawara et al.37 in the synthesis of multiple
ring systems, discussed later. The tin ketyl can be
considered a pseudo-protected radical anion, where the O-Sn
bond has a large degree of ionic character due to
electronegativity differences (Scheme 1-6) The apparent
challenge to synthetic chemists is to develop methodology


9
which exploits both elements of reactivity which are
presented by this radical anion. Some of the work in Chapter
2 will address this challenge.
24 25 26
Scheme 1-6
So far, this dissertation has discussed reductive free-
radical chain reactions and how they can produce carbon-
centered radicals, followed by hydrogen atom abstraction.
The next logical step is to examine their use in the
formation of carbon-carbon bonds, which is particularly
important because carbon-carbon bonds are the heart of
organic synthesis. Before one can use radicals in the
synthesis of complex molecules one must understand the
physical organic principles of free radicals. Some of the
factors which dictate how a radical will react include
orbitals, conformations, thermochemistry, and reaction rates.
The basic premise upon which thermochemistry is built is
that reactions which are exothermic (downhill in energy) are
favorable processes. Very often the behavior of radicals can
be rationalized from this standpoint. A good example is the
well known ability of oxygen-centered radicals to abstract
hydrogen. In this reaction a very strong 0-H bond (-111


10
kcals)3 is formed at the expense of a weaker C-H bond (~99
kcals).3 Because a reaction is exothermic does not guarantee
that it will happen spontaneously, but it can be used as a
guide to see how feasible a transformation is.
The substituents on a radical also have a profound
effect on a radical's behavior. Giese noted that cyclohexyl
radical adds 8500 times faster to acrolein than to 1-hexene.38
In contrast, trifluoromethyl radical undergoes addition
reactions most efficiently with electron rich olefins such as
enamines and enol ethers.2 These results can be explained
using frontier molecular orbital theory.39 The singly
occupied molecular orbital (SOMO) of a radical interacts with
either the lowest unoccupied molecule orbital (LUMO) (Figure
1-2) or with the highest occupied molecule orbital (HOMO)
(Figure 1-3) of the alkene.2 In the trifluoromethyl example,
the inductive, electron-withdrawing effect of the fluorines
lowers the SOMO energy such that there is better orbital
overlap with the low-lying HOMO of the alkene.
C6Hn* SOMO
LUMO
l
EWG
Figure 1-2
Reaction of cyclohexyl radical with electron-poor alkene


11
cf3*
HOMO
l
EDG
Figure 1-3
Reaction of trifluoromethyl radical with electron-rich alkene
Another factor which influences the regioselectivity and
the stereochemistry of radical cyclizations is molecular
geometry. The regioselectivity of radical transformations
often complements or improves on the results which are
available through ionic reactions. 5-hexenyl radicals (29)
cyclize predominately to give five-membered rings (Scheme 1-
7), 40 whereas cationic cyclizations yield six-membered rings.1
Conjugate addition of radicals to activated olefins occurs
solely at the 15-carbon, but anionic conjugate addition often
shows a competition between 1,4 and 1,2 addition.1
Scheme 1-7


12
The stereochemistry of 5-hexenyl radical cyclizations
has been thoroughly investigated by the Beckwith group.41 In
many additions to double bonds, such as cationic, attack
occurs at the center of a double bond, but radical reactions
are generally accepted to proceed via an early, unsymmetrical
transition state.42,43 Beckwith has formulated a model based
on the cyclohexane chair transition state (Figure 1-4) where
major products will be formed from the conformer with
substituents in the equatorial positions (Scheme 1-8).
r 11
Figure 1-4
Beckwith's chair-like transition state
Once the factors which influence radical reactivity have
been considered, the reactions in which they participate can
be examined. These reactions can be divided into two main
categories: intermolecular and intramolecular. The
intermolecular reactions are more difficult to accomplish
because the radicals must find the other reactive partner
before they are reduced by TBTH. This problem can be
circumvented by using either syringe pump or hydrideless tin
techniques to maintain a low hydrogen donor concentration.44


13
Scheme 1-8


14
The most basic intermolecular reactions that can occur
are recombination and disproportionation, which are both
radical-radical reactions. Recombination of radicals has
found some applications in synthetic chemistry. The Kolbe
electrolysis of carboxylate salts can lead to dimerization,45
or mixed couplings if one acid is used in excess.46
Disproportionation is the other pathway that two radicals can
take when they meet. Disproportionation and recombination
both occur when proponic acid is electrolyzed: butane is the
product of recombination, and ethane and ethylene are the
results of disproportionation.
Many intermolecular processes are simple substitution
reactions where the intermediate radical is quenched with
either a hydrogen source or a functional group.
Dehalogenation and deoxygenation reactions have become a
standard reaction in the armory of synthetic chemists2 and
have already been discussed in this dissertation. When the
thiocarbonyl methodology is applied to carboxylic acids, the
carboxylate can be replaced by many groups such as halogens,
chalcogens, and phosphorus groups.2
R
v \ TBTH
R. + \ \
Y
13 44 45
Scheme 1-9


15
The most important intermolecular methodology for the
synthesis of aliphatic carbon-carbon bonds via radical
reactions is the addition of alkyl radicals to alkenes1
(Scheme 1-9). For these reactions to be successful there is
a selectivity requirement which must be fulfilled. The
selectivity requirement pertains to the intermediate radicals
11. 13f and These transient radicals all have specific
partners that they must react with for a successful synthesis
to occur. If 4JL and JL2. have the same tendency to add to
alkenes, then the reaction will result in polymerization.1
This problem can be avoided by careful selection of the
alkene appendage so that 13 and 4 5 have different
selectivities. To avoid polymerization the electronic
characteristics of the substituents on JUL and AJL must be
opposite in nature. An electron donating group on 2, (such
Scheme 1-101


16
as a simple alkyl radical) and an electron withdrawing group
on the alkene is a popular combination (eq. 8). 47 When these
appendages are used X2. becomes a nucleophilic radical which
prefers to add to electron deficient alkenes such as 4 9.
This gives 4_5. (Y=CN) which is now an electrophilic radical
because of the cyano group. Electrophilic radicals favor
adding to electron rich alkenes, therefore it will not add to
4 9 (polymerization) and it will eventually be quenched by
TBTH. Equation 9 shows the other potential combination of
radical and olefin substituents.48
Scheme 1-11
One of the main criticisms regarding radical chemistry
has been that due to the planarity of the intermediates their
application in chiral synthesis is impossible. Motherwell
rebuffs this argument by saying that "the planarity of
enolate anions, iminium ions and even free carbocations has
not hindered the effective operation of stereoelectronic


17
control elements leading to stereospecific reactions."2
Currently there are at least three groups working on the
control of acyclic stereochemistry, where the element of
control centers around the use of a chiral auxiliary on the
alkene. The Porter49 and Giese50 groups use the
dimethylpyrrolidine 1, and Curran and coworkers51 use sultam
55 as their chiral auxiliary. Scheme 1-12 shows how Porter,
Scott, and McPhail used the dimethylpyrrolidine auxiliary to
control the addition of cyclohexyl radical to alkene Jjji which
produced JL2. as the only diastereomeric product.52
Figure 1-5
Chiral auxiliaries used by Porter, Giese, and Curran
hv
-78C
58
Scheme 1-12


18
The intramolecular reactions that radicals can undergo
can be grouped into two different categories: rearrangements
and cyclizations. Rearrangements can take on many forms
ranging from simple hydrogen abstraction to
cyclopropylcarbinyl rearrangements. A popular intramolecular
reaction of radicals is a 1,5-hydrogen migration, which
proceeds through a six-membered transition state.53 An
interesting example of this reaction is by Rawal and
coworkers54 who recently reported the transformation shown in
Scheme 1-13. The olefin that is formed when the epoxide opens
eventually cyclizes with the carbon radical that is
Scheme 1-13


19
formed when the alkoxy radical abstracts a hydrogen from the
5 carbon. The analogous 1,5-tin migration will be the
subject of Chapter 3 of this dissertation.
Carbon-carbon bonds can also be fragmented using
radicals. When a radical is generated a to a cyclopropane it
rapidly equilibrates to its homoallylic counterpart.2 This
ring-opening reaction has been used by Motherwell and
Harling55 to build bicyclospiro fused compounds (Scheme 1-14).
The radical which is formed by the fragmentation of the
thiocarboxylate opens the cyclopropane ring. This radical
then cyclizes onto the suitably disposed alkyne, and the
vinyl radical is eventually quenched by TBTH.56
Scheme 1-14
As you can see from the examples above, radicals can
abstract hydrogens and fragment C-C bonds, but their main
function often lies in cyclization reactions. This thesis
will examine how carbonyls can be used to generate carbon-
centered radicals and the cyclizations that the resultant
radicals undergo. Prior to Enholm's studies very few papers


20
approached these reactions from a reagent-based standpoint.
The photolysis57 and electrochemistry5 of ketones differ from
the studies in this dissertation in that both are nonreagent
based methods which will be only briefly reviewed here.
When carbonyls are irradiated with light, an n-Jt*
transition occurs in which an electron from the nonbonding
orbital on the oxygen is promoted to 7t-antibonding orbital of
the ketone. The carbonyl in its excited state can either
abstract a proton from the solvent or an available hydrogen
donor, or it can fragment to give more stable molecules.
Fragmentation reactions can be divided into two categories,
type-I and type-II, based on the work of Ronald Norrish who
shared the Nobel prize in chemistry in 1967. In type-I
fragmentation reactions a carbonyl substituent is cleaved to
produce acyl and alkyl radicals. In most cases the acyl
radical is cleaved again to generate another alkyl radical
and carbon monoxide. The photolysis of £7. by Quinkert and
coworkers59 demonstrated this reaction, where subsequent
cleavage of the carbonyl appendages produced carbon monoxide
and a diradical species which coupled with itself to form iLS..
Scheme 1-15


21
The second type of Norrish cleavage happens when the
carbonyl compound being irradiated contains hydrogens on the
8-carbon. In this reaction the photoexcited carbonyl
abstracts a hydrogen from the 5-carbon through a six-membered
transition state to give a carbon-centered radical. The
diradical which is produced, 72. can either fragment to give
7 4 and 7 5 or couple to yield cyclobutanols.60 These
fragmentations can be distinguished by the bonds which are
broken. In type-I reactions the bond between the carbonyl and
the a-carbon is ruptured, but in type-II the Ca-Cp bond is
broken.
OH
7 3
7 5
Scheme 1-16
The electrochemistry of carbonyls has also shown that
they can effectively act as radical precursors.58 When
conducting solutions of ketones and aldehydes are
electrochemically reduced, there is a competition between
reduction to the alcohol and coupling of the intermediate


22
radical to give pinacol products. In recent years, however,
there have been successful attempts to trap the ketyl
radicals with a variety of appendages, such as alienes,
alkenes, alkynes (Scheme 1-17),61 and even benzene rings.58
The nature of the reactive species is sometimes clouded by
the conditions of the reaction, but it is generally believed
that either a ketyl (radical anion) or a protonated ketyl is
the reactive intermediate.
Scheme 1-17
Although sparse, there were two reports of the O-stannyl
ketyls being used in free radical cyclizations. In the
first, Beckwith and Roberts36 showed that tin ketyls can be
used to assemble bi- and tri-cyclic systems. The cyclization
(Scheme 1-18) proceeded with excellent yield, but they
remarked that the reaction was "sluggish" and required
additional TBTH and AIBN. Beckwith speculated that the
formation of the tin ketyl may be reversible or that either
the rate of the radical's initial formation or its subsequent
cyclization was slow. More likely, the problem with this
cyclization is that the nucleophilic tin ketyl would prefer
to react with a more electrophilic double bond.


23
90%
Scheme 1-18
More recent research indicates that cyclizations of tin
ketyl are effective and have potential applicability in
synthesis. In a second paper which preceded this work,
Sugawara and coworkers37 may have realized that an activated
alkene would solve the problems that Beckwith observed. They
used tin ketyls in the cyclization of aldehyde Q. onto the
activated olefin of a uridine ring system (Scheme 1-19).
Note that in this example, the skeleton is constrained to
prepare a six-membered ring, and the 6-exo closure of the 6-
heptenyl radical is known to be more than one order of
magnitude slower than the analogous 5-hexenyl cyclization.62
So an activated alkene is sometimes crucial to the success of
a radical cyclization.
Aside from these two synthetic reports, only the Enholm
group is actively reporting on studies directed towards the
use of tin ketyls in synthesis. This interest began in 1989
when Enholm and Prasad63 demonstrated that aldehydes and
ketones readily cyclized onto tethered olefinic appendages.
Although an unactivated olefin did cyclize, the yield was


24
low, and to achieve a synthetically useful yield the olefin
needed electron withdrawing groups, i.e., activation. They
also demonstrated the 6-exo cyclization of an activated
olefin, as shown in Scheme 1-20, where they produced cyclized
products in a 69% yield.
Scheme 1-19
Scheme 1-20
The next step for the Enholm group was to see if tandem
cyclizations were possible with tin ketyls. Enholm and
Burroff64 found that both spiro and fused bicyclic ring
systems could be synthesized with this methodology. In this


25
study activated olefins were used in the first cyclization
and unactivated olefins were used in the second cyclization.
The activated olefin which is involved in the first
cyclization must act as both an acceptor and a donor in this
reaction. Also notice that intermediate radical 8 6 is
electrophilic and therefore needs a nucleophilic olefin for
effective cyclization. All of these criteria are met and the
reaction proceeds smoothly to give bicyclic products in a 75%
yield.
85 86 87
Scheme 1-21
This dissertation investigated the free radical behavior
of tin ketyls which are functionalized so that the radical
could be delocalized or separated from the carbonyl. This
was accomplished by the use of unsaturated and epoxy ketones.
TBTH was used to generate the tin ketyl, and activated and
unactivated olefins were used to trap the radical
intermediates.
In Chapter 2 the behavior of a,(3-unsaturated ketones and
their cyclizations and additions to activated olefins was
examined. Highly functionalized monocyclic and bicyclic


26
cyclopentanes were obtained. An interesting concentration
effect was observed which can be attributed to the
reversibility of the cyclization. This concentration effect
enabled the reactions to achieve excellent
diastereoselectivities (>50:1). Both intramolecular and
intermolecular additions were examined and their
applicability towards five-membered ring natural products was
considered.
Chapter 3 continues to examine the reactivity of the tin
ketyl with labile a-substituents. The reactions of a,(3-epoxy
ketones with TBTH and their subsequent cyclizations onto
unactivated olefins were examined. These reactions, which
could form tetrahydrofuran products by addition of oxygen-
centered radicals to olefins, were found to undergo an
unusual 1,5-tin transfer to yield carbon radicals. These
radicals were useful, though, and underwent cyclizations to
create highly substituted cyclopentanes.
Once thought to be too unruly for the delicate world of
synthetic organic chemistry, free radicals have exploded onto
the scene. These intermediates have been generated under
mild conditions, have been shown to be very selective, and
have tolerated a wide range of functionality. Their
viability as a powerful synthetic intermediate has been
proven by Dennis Curran and others who have synthesized
entire families of natural products with these species. TBTH
has shown that it is a valuable synthetic reagent for a
variety of transformations. This work attempts to


27
demonstrate that carbonyls can be used effectively as radical
precursors with a flexibility that has not been illustrated
by either electrochemistry or photochemistry.


CHAPTER 2
CYCLIZATIONS OF a,P~UNSATURATED KETONES
The foundation for this project was established in 1989
by the work of Enholm and Prasad.63 They studied the
cyclizations of O-stannyl ketyls £_2. onto both activated and
unactivated olefins (Scheme 2-1) The stereoselectivity of
the ring closure ranged from 1:1 (antirsyn, relative to the
hydroxyl) to 3:1. A natural extension of this work was to
attach appendages to the O-stannyl ketyl and see if the
radical could be separated from the oxyanion by resonance.
The work presented in this chapter was published in a
preliminary form as a JACS Communication in 1991.65
Rx = Hydrogen or Alkyl
R2 = Alkyl or EWG
Scheme 2-1
An unsaturated appendage seemed a natural selection due
to many factors, which included ease of preparation and
28


29
effective delocalization through resonance. The general
transformation, shown in Figure 2-1, would involve the
coupling of the (3-carbons of dieneone 91 This is a
difficult coupling because the ^-carbons in this system both
carry a partial positive charge. Prior to our studies there
were no reagent-based methods to accomplish this
transformation,66 but there were electrochemical methods.58'67
Figure 2-1
General transformation of a,(3-unsaturated ketones
These methods suffer from some of the basic drawbacks
that are associated with electrochemistry. Only conducting
solvent systems can be used, and this is usually limited to
CH3CN/H2O. The conditions need to be closely controlled to
avoid unwanted pinacol and aldol products. Aldol and
saponification (EWG = CO2R) products result because basicity
builds up at the cathode. Often the specialized equipment is
not readily available to a practicing synthetic organic
chemist, or it may be expensive. Lastly, this method is not
selective enough to be applicable to natural product
synthesis which may contain numerous labile functional
groups. The stereoselectivities obtained are usually low, 2:1


30
(anti:syn), although in a single report, Little and Baizer67a
observed that the addition of CeCl3 improved
stereoselectivities (Scheme 2-2).
Without CeCl3
With CeCl3
2.6 to
15 to
1
1
Scheme 2-2
Electrochemists have provided some interesting details
on the physical properties of the radical anion ESR spectra
of enones, which do not possess acidic hydrogens. These
studies show that 50% of the radical density is located on
the P-carbon 22. (Figure 2-2), while the remaining portion is
divided equally between the carbonyl carbon 9 6 and the
carbonyl oxygen 95.66a' 68
O* O' O
95 96 97
Figure 2-2
Major resonance contributors for the enone radical anion


31
Our studies were initiated by addressing the question of
whether we could obtain an efficient cyclization with
substrates such as 8. where the carbonyl is replaced by an
a,P-unsaturated ketone to prepare _2_1. The ketyl, which is
produced by the reaction of enone 9 8 with tributyltin
radical, has two major resonance contributors 33 and 100. One
might speculate that, if an analogy with the electrochemical
resonance structures can be drawn, then 100 should be the
major contributor. Also, electronegativity differences
between 0 and Sn should make radical 100 electron-rich. As
mentioned before, an electron-rich or nucleophilic radical
will prefer to react with an electron-deficient olefin.1
It was first necessary to determine whether activation
of the olefin was essential for a successful cyclization.
When 101 was subjected to radical cyclization conditions the
only product 102 which was observed was a result of simple
reduction of the conjugated olefin. These results were not
surprising considering that the radical reduction of (X,P~
unsaturated ketones is a precedented reaction.69 We had hoped
that both activated and unactivated olefins could be used in


32
this study, but this result showed that an activated alkene
was a critical element for success.
C5H11
92%
Scheme 2-4
The reason why this cyclization did not work is
supported by the frontier molecular orbital theory which was
presented in Chapter 1. Enholm and Prasad63 also found that
tin ketyls were reluctant to cyclize with unactivated
olefins. The tin alkoxylate in both of the intermediate
radicals 2A and 100 impart some negative character onto the
radical, which raises the energy of the SOMO. Higher energy
SOMO's have better orbital overlap with the LUMO's of
electron deficient olefins (Figure 1-2) .2 It is apparent
from these cyclizations that the intermediate radical did not
effectively cyclize and was quenched by TBTH. Therefore, the
rate of cyclization with unactivated alkenes is slow relative
to the rate of hydrogen abstraction..
Once it was determined that an activated olefin was an
important prerequisite for successful cyclizations, our
attention was then focused on the synthesis of the required
starting materials. Glutaric dialdehyde 103 seemed ideally


33
suited for the two-step attachment of unsaturated appendages.
But, what seemed to be a trivial Wittig reaction to make
aldehyde 104 became somewhat of a challenge due to the
predominance of the di-addition product. When 1 equivalent
of Wittig reagent was added by addition funnel to a large
excess (4 eqs.) of dialdehyde the product ratio still favored
the bis-product 7:1 (di:mono) This was only a minor
inconvenience because the di-addition product 106 was one of
the intended starting materials. Eventually, the slow
addition of ylide (1 eq.) by addition funnel to 7 eqs. of 103
gave the desired mono-addition product 104 in 74% yield. The
second unsaturated appendage was added without problems to
yield the needed starting materials (Scheme 2-5).
O
O
EWG
103
104
105 106 107
74%
EWG= -CN, -COMe, -CO?Me
47%, 52%, 49%
Scheme 2-5
In a typical cyclization, the unsaturated ketone was
dissolved in benzene (0.1 M) then 3 eqs. of TBTH, and 0.1
eq. of AIBN were added. The mixture was degassed with Argon


34
105
TBTH,AIBN
C6H6,80C
108
3.0
to 1
(94% Yield)
TBTH,AIBN
C6H6,80C
106
COMe
110
3.5
to 1
(93% Yield)
TBTH,AIBN
C6H6,80C
OMe
(85% Yield)
Scheme 2-6


35
and then heated to 85C (bath temp.) The reactions were
monitored by thin layer chromatography (TLC), and in most
reactions the starting material was consumed within two
hours. These reactions never seemed to suffer from the
sluggish behavior that Beckwith reported,36 and they were also
very clean reactions. A summary of the results of these
cyclizations and their products are shown in Scheme 2-6. The
ratios and yields reported are from the isolated products and
are in good agreement with the GC ratios.
The proposed mechanism for these reactions is presented
in Scheme 2-7. The initiation steps which produced
tributyltin H radical were covered in Chapter 1, Scheme 1-2,
and will not discussed further here. Tributyltin radical H.
added to the ketone carbonyl of the starting material to
generate the O-stannyl ketyl 115. This ketyl radical, in
conjugation with the allylic double bond, has a resonance
form with the radical at the [5-carbon 116. This resonance
form, a 5-hexenyl radical, subsequently cyclized with the
activated olefin. The resultant radical species 117
underwent hydrogen atom transfer with a second molecule of
TBTH, generating another tributyltin radical which continued
the chain process. Tin enolate 118 was then quenched by a
proton source to yield the final cyclized product 119.
The minor bicyclic syn products were formed by a second
cyclization. The EWG used to activate the olefin could also
undergo a second intramolecular reaction with the tin
enolate, as in 121. When the appendages were anti to one


36
another they were not close enough to react and the anti-ring
fusion in 118 is too strained,70 but when they were syn a
second aldol-like cyclization occurred (Scheme 2-8). These
products demonstrate that the dual reactivity of tin ketyls
can be utilized. They undergo an efficient radical reaction
followed by a smooth two electron condensation reaction.
Scheme 2-7
120 121 122
Scheme 2-8


37
Structural identification of the bicyclo syn products
was not always a trivial pursuit. It was believed that the
bicyclo syn product 109 from the cyclization of nitrile 105
would be an imine which could be hydrolzed to 113.
Unfortunately, this compound resisted attempted hydrolysis
with 1 M HC1. After comparison with standard library spectra
and conversations with Dr. John Greenhill it was decided that
the actual structure was the keto-eneamine shown in Scheme 2-
6.
The syn product from the cyclization of ester 107 was a
1,3-diketone. The literature H1 NMR spectra of 2-
acetylcyclopentanone showed contributions from all three
tautomeric forms (Scheme 2-9) 123 was the most stable form
and has a methyl group at 1.94 ppm. The methyl group of 125
was assigned a chemical shift of 2.21 ppm, and the enolizable
proton was barely visible at 3.35 ppm. 113 had a very strong
singlet at 2.06 ppm, and a very small singlet at 2.22 ppm,
where the ratio is about 10:1 respectively from 1H NMR
integration. This analogy was not strong enough to
accurately identify the tautomer, therefore, its structure
was unknown.
Scheme 2-9


38
Proton (s)
Percent Effect Observed
Irradiated
Ha
HB
HC
Hrf
H6H
ch3(A)
CH3(K)
Ha
30.1
6.0
2.7
2.1 *
Hb
26.1
6.0
He
2.8
7.8
2.5
*
Hrf
1.5
7.2
0.76
H6H
CH3(A)
*
2.8
2.2
CH3(K)

2.4
3.01
* = Proton difficult to observe due to proximity with irradited proton.
1 = Molecule can adopt a conformation which could give these results.
Figure 2-3
Difference NOE data for 111


39
The syn product 111 from the cyclization of ketone 106
was surprisingly isolated as a single diastereomer. The
structure was confirmed by extensive NOE difference studies
summarized in Figure 2-3. Additionally, the hydroxyl
proton's chemical shift was independent of the concentration
of the sample. Therefore, it was believed to be
intramolecularly hydrogen bonded to the ketone. It is
interesting to note that in this product, four stereogenic
centers were created, however only isomer 111 was observed.
Particularly disturbing to us was the anti
stereochemistry of the appendages which stood in marked
contrast to nearly all other 5-hexenyl radical
cyclizations. 2'13 Normal radical cyclizations which produce
substituted cyclopentanes conform well to the classic
Beckwith model.40 Beckwith's model (Fig 1-4) suggested that a
1-substituted 5-hexenyl radical gave mostly syn products; our
results conflict with his model. An explanation of these
deviations are based on several differences between the two
radical chair-like systems. Beckwith's system (Scheme 1-8)
involved the cyclization of a radical with an alkene trap,
and essentially this reaction is kinetically controlled and
irreversible. The product ratio was determined by which ever
isomer formed the fastest, and was said to be under kinetic
control. However, our cyclization involved a resonance
stabilized allylic radical reacting with an activated olefin.
The resonance stabilization of this radical made the reaction
reversible and allowed the less stable syn product to


40
equilibrate and form the more stable anti isomer; this is
thermodynamic control. It could also be argued that the high
degree of polarity that 105-107 possesses is not adequately
represented by the bare skeleton of Beckwith's model.
If our system was indeed under thermodynamic control,
then we believed that varying the concentration and the
amount of TBTH would lead to improved stereoselectivities.
When the reaction was examined at greater dilution, we were
delighted to obtain much higher levels of stereoselectivity.
Thus, 107 was cyclized at three different dilutions as shown
in Scheme 2-10. Increasing levels of anti-stereoselectivity
for the ring appendages were obtained as the reaction was
diluted. A ratio of greater then 50:1 for the anti:syn
products could be achieved at 0.01 M in benzene.
C02Me
113
Reaction Conditions 112:113 (% Yield)
1.
1.00
M
in
benzene,
rH
tH
eq.
TBTH
9:1
(75%)
2 .
0.10
M
in
benzene,
1.1
eq.
TBTH
25 :1
(82%)
3 .
0.01
M
in
benzene,
1.1
eq.
TBTH
>50 :1
(82%)
Scheme 2-10


41
This dramatic increase in anti-stereoselectivity can
likely be attributed to the reversibility of the cyclization
and the decreased availability of TBTH. Once the cyclized
radical 117 reacted with a second molecule of TBTH it was no
longer able to open up to 116. Making the reaction more
dilute and decreasing the equivalents of TBTH allowed the
intermediate radical 117 more time to equilibrate before it
was quenched. By the time the radical was quenched the
equilibrium would have shifted from the kinetic syn product
to the thermodynamic anti product.
It could be that Beckwith's model was applicable to this
system, and that with even more concentrated solutions and an
excess of TBTH the syn isomer could be the major product.
However, it is difficult for a intermolecular quench to
compete with an intramolecular equilibrium and it is doubtful
that these conditions could be found. The more likely
scenario was that Beckwith's model was not entirely
applicable to this very polar substrate, and that ratios
observed at high concentration may be the kinetic product.
Regardless, the dilution study showed that this reaction was
reversible and that excellent anti-stereoselectivities could
be achieved.
Now that the one-electron chemistry of the tin ketyl had
been explored, we attempted to establish the ability to
conduct two-electron chemistry as well. Although this has
already been demonstrated by the isolation of the minor
bicyclic products, two additional experiments were performed


42
which clearly establish the presence of the stannyl enolate.
Since these reactions were not run in a strictly tandem
sequence, we use the term "serial reactions" to refer to
these studies. In each experiment, the one-electron
reactivity of an allylic O-stannyl ketyl was induced to
cyclize under the dilute anti-selective conditions (run # 3)
as shown in Scheme 2-10. The resultant tin enolate was then
immediately quenched in the same pot with Br2 or D2O to
produce a ca. 2:1 mixture of 12 6 and 127 as shown in Scheme
2-11. From ^-H NMR integration of the methylene group a to
the ketone deuterium incorporation was calculated to be
greater then 85%.
OMe
1.TBTH,AIBN
^6^6,A
2. Quench with
Br2 of D20
126 Z=Br (86%)
127 Z=D (87%)
Scheme 2-11
These results and those for the previously discussed
bicyclic products clearly demonstrated the presence and
utility of the tin enolate. Also the monocyclic products and
dilution studies showed that the radical cyclization of
allylic O-stannyl ketyls could be both efficient and highly
stereoselective. Collectively these studies show that the


43
one-electron reactivity in the allylic O-stannyl ketyl can be
separated from the two-electron chemistry by sequential
transformations, and by the correct choice of experiment.
Thus, both types of reactivity can be achieved.
Now that the effectiveness of a,(3-unsaturat ed ketones
was demonstrated on an intramolecular level, the next task
was to see if it was equally effective on an intermolecular
basis. The electrochemistry of a,P~unsaturated ketones has
shown that intermolecular coupling is a promising route to
highly functionalized cyclopentanes, and they have termed
these reactions electrohydrodimerization EHD. 58, 6"7 This name
was derived from the overall transformation where the
products represented dimerization of the starting material
with the addition of two hydrogens.
Often many problems are encountered when one goes from
intramolecular reactions, where the course of the reaction
can be controlled by the prudent selection of starting
materials, to intermolecular reactions which have a great
deal of freedom to react along many different pathways.
Coupling of unsaturated ketones could occur from both the
carbonyl carbon (head) and the P~carbon (tail) This meant
that three different coupling products were possible: head to
head (pinacol), head to tail, or tail to tail. The
hydrodimerization of enone 128 (Scheme 2-12) exemplified the
frustrating product mixture which could be produced.71
Electrochemists believe that these reactions go through


44
either the combination of two radical anions or the addition
of a radical anion to the starting enone.67c
0
128
e ,CH3CN
Bu4NBF4
52% 31% 16%
Scheme 2-12
A preliminary attempt to hydrodimerize methyl vinyl
ketone under radical conditions produced a low yield of a
compound whose 1H NMR spectra resembled an
acetylcyclopentanol. This hydrodimerized product further
reacted through its tin enolate to give the cyclopentanol.
The hydrodimerization of cyclohexenone resulted in the
recovery of 37% of the starting material's mass in form of
hydrodimerized products. The failure of these reactions to
achieve usable yields was most likely due to either the
volatility of the starting materials and products or the
lifetime of the radical was not long enough to allow for
coupling.
Both of these potential problems were circumvented in
the hydrodimerization of trans-chalcone 132 The reaction
conditions and product ratios are shown in Scheme 2-13.


45
Notice the delicate balance that existed between the
concentration and the equivalents of TBTH. Reaction 1 showed
that, if too much TBTH was used, simple reduction of the
olefin would be the major product 13 5 In an effort to
increase the amount of hydrodimer 134 that was formed, the
reaction was run at even higher concentration with the
minimum amount of tin required. We were delighted to find
that the previous ratio was reversed and that we were able to
isolate hydrodimer 134 in a 72% yield. It was isolated as an
inseparable mix of isomers whose spectra and melting point
agreed with published reports.72
132
133
134
Reaction Conditions 133:134 (% Yield)
1.
0.5
M
in
benzene,
1.50
eq.
TBTH
4 : 1
(93%)
2 .
1.0
M
in
benzene,
0.55
eq.
TBTH
1:3
(94%)
Scheme 2-13
A proposed mechanism for the hydrodimerization of trans-
chalcone is shown in Scheme 2-14 13 4 was formed by the
initial P-P coupling of the allylic O-stannyl ketyl 135 with


46
a molecule of trans chalcone, and resultant radical 136 was
quenched with TBTH to give tin enolate 13 7. This enolate
then condenses int ramolecularly on the ketone to give tin
alkoxide 138 that upon hydrolysis yielded the final
hydrodimer 134.
0
OSnBu3
Bu3Sn 132
Ph
Ph
Ph
134
138
Scheme 2-14
137
Although hydrodimers were achieved by this method it was
believed that the scope of this reaction was not sufficiently
broad to make it synthetically useful. Stabilization of the
allylic O-stannyl ketyl radical with phenyl groups seemed to
be imperative to the success of this reaction. The tentative
balance between reaction concentration and TBTH concentration


47
also limited this reaction. This problem could be avoided by
the use of either hydrideless tin sources or syringe pump
techniques. Both of these methods keep the concentration of
hydride donor at very low levels, but if these reactions were
run at high reaction concentration and low hydride density
then the most likely products would be polymers.
In conclusion, the intramolecular coupling of 0C,(3-
unsaturated ketones to activated olefins can be applied to
the synthesis of substituted cyclopentanes. Excellent anti
stereoselectivities can be achieved with the proper selection
of reaction conditions. Additionally, the dual reactivity of
the allylic O-stannyl ketyl radical can be separated and
utilized in sequential one- and two-electron reactions.
Although, the intermolecular coupling of unsaturated ketones
was demonstrated, additional work is needed for this
methodology to be synthetically useful. This additional work
should be focused on hydrideless tin and syringe pump
techniques, also the prospect of cross-coupling reactions
should be investigated. Collectively, this work has
illustrated that a,p-unsaturated ketones are a viable radical
precursor, and the degree of functionality and stereocontrol
which can be achieved allows this methodology to be applied
in the synthesis of natural products.


CHAPTER 3
CYCLIZATIONS OF a,(3-EPOXY CARBONYLS
In continuation of our studies directed towards the use
of carbonyls as free radical precursors, we examined the free
radical ring-opening reactions of epoxy ketones and
aldehydes. The radical ring opening of cyclopropanes is
known to be an extremely rapid process,73 likewise, the
analogous opening of epoxides is thought to be equally
rapid.2 The main difference between these two system is the
radicals which can be produced. The cyclopropyl case can
yield only carbon-centered radicals, while the epoxide
example can afford either oxygen-centered or carbon-centered
radicals, depending on which bond of the epoxide fragments.
The direction of fragmentation is largely controlled by
the nature of the Ri substituent (Scheme 3-1) Jorgensen74
has suggested that the bond dissociation energy of the C-0
bond is lower than the C-C bond except when stabilizing
groups are present to lower the energy of the C-C bond. When
this is a radical-stabilizing group such as a vinyl or aryl
group, then fragmentation of the C-C bond leads to a low
energy and delocalized carbon-centered radical. When no
stabilizing groups are present, cleavage of the weaker C-0
bond will be the predominant reaction. Synthetic methods
48


49
have been developed which utilize both of these fragmentation
pathways.
Ri
141
C-C Bond
Cleavage
C-0 Bond
Cleavage
Ri
143
Scheme 3-1
The route which has received the least attention has
been the fragmentation of the carbon-carbon bond to give
stabilized radical 141. The reason why there has been less
research focused on this methodology is because the
requirement of a radical stabilizing appendage tends to limit
its applicability. Additionally, some researchers have found
that the presence of either vinyl75 or aryl76 substituents do
not guarantee the formation of carbon-centered radicals.
But, it is generally accepted that the presence of these
groups will lead to cleavage of the C-C bond.77
Feldman and Fisher75 used this fragmentation to generate
functionalized THFs. Radical 147 was generated by addition
of phenylthio radical to epoxyalkene 144. The epoxide ring
was opened by cleavage of the C-C bond to give stabilized
radical 148. which reacted with the activated olefin to give
adduct 149. This radical then cyclized onto the olefin which
was created by the epoxide opening, and the final product was
produced by elimination of thio phenyl radical.


50
<^ 0
EWG
144
145
Ph2S2, AIBN
CgHg, hV
147
-PhS
148
SPh
Ar
Scheme 3-2
The syn-2,5 products were the only diastereomers which
were observed, and this conformed to the stereochemistry
which was predicted by Beckwith's model (Figure 1-4). Very
little control at the C-4 position was demonstrated, but this
can be blamed on the epimerizability of this center and not
necessarily on the cyclization. This reaction represents a
formal [3 + 2] addition where essentially both electrons of a
carbon-carbon bond are used to make the new bonds. This is a
very interesting approach to the synthesis of THFs and
demonstrates that all retrosynthetic disconnections should be
explored.
The majority of the classical work in the late 1960s and
early 1970s dealt with the opening of epoxides, mostly
concerning the pathway which produced oxygen-centered radical
143. In these papers, there are a wide variety of methods


51
for the production of the a radical, and many different
synthetic and mechanistic goals. The common thread which
runs through these papers is that a radical is generated a to
an epoxide which causes the epoxide ring to open, and the
resultant alkoxy radical helps accomplish their
transformation. Some of this work, which pertains to this
dissertation, will be reviewed here.
If radical 143 was simply quenched by hydrogen atom
transfer with TBTH then allylic alcohols would be the
product, and many papers have utilized the fragmentation in
this manner.78 This transformation could be thought of as a
convenient alternative to the Wharton reaction,79 where epoxy
ketones were reacted with hydrazine to give allylic alcohols.
It was discovered in 1971 by H. C. Brown and coworkers78a when
alkyl radicals from organoboranes added to vinyl epoxides to
form allylic alcohols.
More recently in 1981, Barton and coworkers78b found that
product formation was highly dependent on the reaction
conditions. The fragmentation of epoxide 151 under "normal
addition" conditions did not give the expected allylic
alcohol as the major product, but instead, gave ketone 153
which resulted from an alkyl migration caused by P~scission
of the C-C bond. "Normal addition"80 refers to TBTH and AIBN
being added dropwise to a refluxing solution of starting
material, which effectively maintains a low concentration of
hydride donor. This low concentration of hydride donor
allows the intermediate radicals to do other chemistry.


52
S N x N
W
151 152 153
Reaction Conditions 152:153 (% yield)
1. 2
eqs .
TBTH,
Normal Addn.
1 : 2.0
(71%)
2. 9
eqs .
TBTH,
Inverse Addn.
4.3 : 1
(72%)
Scheme 3-3
Barton
and
coworkers felt that,
if they could
maintain a
very high concentration of hydride donor, they would be able
to isolate the allylic alcohol in useful yields. The
"inverse addition" method that they used maintained a very
high concentration of TBTH by dropwise addition of the
starting material to a refluxing solution of TBTH (9 eqs. )
and AIBN. The high concentration of hydride donor quenched
the intermediate alkoxy radical before it could do other
chemistry. Other examples in this paper showed that "inverse
addition" helped avoid unwanted side reaction products which
were formed when the "normal addition" method was used.
However, these unwanted products showed that alkoxy radicals
can do a great deal more then simple hydrogen abstraction,
and groups began to explore their potential.


53
Johns and Murphy81 were intrigued by some of the
products which were described in Barton's paper and set out
to see if the alkoxy radical could be used in the synthesis
of tetrahydrofurans. Starting material 15 4 is easily
prepared from commercially available geranial. To keep the
concentration of TBTH at a low level they used the "normal
addition" process and isolated THF products in pretty good
yields (Scheme 3-4) Although no ratios were given, they
mentioned that in the R=n-butyl case, the major diastereomer
had an anti-relationship between the vinyl and the isopropyl
group, which was in agreement with the major products formed
in Beckwith's studies (Scheme 1-8). Interestingly, bicyclic
product 156 was formed by a tandem radical cyclization where
the radical formed after the first cyclization reacted with
the vinyl group in a second cyclization.
Scheme 3-4


54
Alkoxy radicals are well known for their ability to
abstract hydrogen atoms through a six-membered transition
state from neighboring atoms which bear hydrogens, which was
demonstrated in the classic Barton reaction.82 There was no
mention of any products derived from this pathway in the
reduction of 154. The only hydrogens which could have been
abstracted through a six-membered transition state were next
to the olefin, and these were not accessible due to the trans
geometry of the olefin. However, some studies have used this
prominent reaction of alkoxy radicals to generate polycyclic
compounds.
Rawal and coworkers54 used the hydrogen-abstracting
ability of alkoxy radicals to facilitate the cyclization
shown in Scheme 3-5. Addition of tributyltin radical to the
thiocarbonyl of 157 caused it to decompose to radical 160.
The epoxide ring was then cleaved by this radical to produce
alkoxy radical 161. which then abstracted a hydrogen atom
from the 5-carbon. The resulting stabilized radical 162 was
then in position to cyclize onto the olefin produced from the
fragmentation of the epoxide.
Bicyclic products were formed in a 69 % yield, and the
ratio between the diastereomers 158:159 was 2.7:1. Product
159. which has the ester pointing into the cup of this cis-
fused bicyclic, was epimerized to the more stable 15 8 by
treatment with catalytic amounts of t-BuOK. This method also
produced successful cyclizations on other cyclic and acyclic


55
systems. Good results were also achieved when alkyl
appendages, with no radical-stabilizing groups, were used.
C02Me
158
159
162
Scheme 3-5
Kim and coworkers83 used the addition of tributyltin
radical to vinyl epoxides in much the same way. The addition
of tin radical to the vinyl group of 163 provided the radical
which opened up the epoxide, which then abstracts a hydrogen
from the 5-carbon. This radical then cyclized back onto the
olefin which was created when the epoxide was fragmented, and
the final product is formed by ejection of tributyltin
radical. Kim's group also had success with alkyl appendages
that contained both electron withdrawing and electron
releasing substituents.


56
Scheme 3-6
In the same paper, Kim and coworkers reported similar
cyclizations which occurred through a rare 1,5-tin transfer.
This mechanism was first proposed by Davies and Tse84 who did
ESR spectroscopy on the reactions of glycidyl tributyltin
ethers 165 with t-butoxy radicals. These studies found that
the predominant radical in solution was 168. The authors
reported that this was the first time that a 1,5-
organometallic transfer had been observed. This mechanism
seemed suspicious at first, but we now believe that our
reactions are occurring by the same mechanism, which will be
discussed later.
165
M = SnBu3
R = H or alkyl
168
Scheme 3-7


57
Other mechanistic studies have looked at the radical-
induced opening of epoxides from another angle. These papers
were more concerned with the stereoelectronic factors which
governed the opening of epoxides. Bowman and coworkers5 used
the norborane skeleton as a template for their reactions.
They envisioned that the exo-oxiranes 169 would lead to C-0
bond cleavage products 111, while the endo-oxiranes 172 would
produce C-C bond fragmentation products 174. This prediction
was based on the stereoelectronic control observed for the
radical ring opening of analogous cyclopropyl and cyclobutyl
systems.86 It was proposed that the transition state required
maximum overlap of the radical's SOMO with the a-bond which
was undergoing scission.
O
169
170
171
172
173
174
R = H or OSnBu3
Ri = H or Aryl
Figure 3-1
Stereoelectronic model for Exo- and Endo-epoxides


58
Bowman and coworkers envisioned this system as the
perfect test for these stereoelectronic factors. Many of the
current papers dealing with epoxide openings invoke this as a
potential mechanism, but it had never been tested. However,
Bowman found that no stereoelectronic effect could be
observed. When aryl derivatives of 16 9 and 17 2 (R=H and
Rl=Aryl) were generated from the corresponding bromides, no
products from the cleavage of the C-0 bond could be isolated.
Additionally, when non-aryl derivatives of 169 and 172
(R=0SnBu3 and Ri=H) were created from the corresponding
ketones, no products from the cleavage of the C-C bond could
be found. They concluded that no stereoelectronic effects
were operational, and that the determining factor was the
strengths of C-C and C-0 bonds.
Many of the twists and turns which were observed in the
works reviewed above, also found their way into the study
which is presented in this chapter. Many of these diversions
were fully anticipated because of the well-known ability of
alkoxy radicals to abstract hydrogen atoms. However, what
was not anticipated was that the rare 1,5-tin transfer
mechanism would be the proposed mechanism. This project
started out as an extension of my oral research proposal,
which presented the idea of synthesizing THFs, such as 175.
through the fragmentations of epoxy ketones. However, the
fragmentation of epoxy ketone 176 which wasused in this
project ended up yielding cyclopentanols 177 .


59
R = H, Me, n-Bu
Scheme 3-8
The molecule which is shown in Scheme 3-8 was very
similar to the system which Johns and Murphy81 used to
synthesize tetrahydrofurans in Scheme 3-4. The only
difference between the studies was that they used
thiocarbonyls to generate the radical and we used ketones.
One would expect that minor differences, such as the
generation of the initial radical, would have little effect
on the outcome of the reaction. However, so often when you
least expect something unusual, that is exactly what you get.
Anyway, we embarked on the study of the free-radical
fragmentation of epoxy ketones, with the hope of developing
methodology related to their cyclizations.
The synthesis of the starting materials for this study
were prepared from geranial, which either could be purchased
or was easily prepared by oxidation of geraniol, and is shown
in Scheme 3-9. The geraniol which was commercially available
was a mixture of cis and trans isomers in about a 1:2 ratio,


60
respectively. No attempt was made either to separate them or
to examine their individual reactivity.
R
177
178
R = Me
179
95%
= nBu
180
96%
R R
Me
182
71%
R = H
185
27%
nBu
183
39%
= Me
186
80%
= nBu 187 98%
Scheme 3-9


61
The allylic oxidation of geraniol 177 proceeded smoothly
to produce geranial 178 in 90% yield. The 1,2 addition of
organolithiums to geranial was carried out at 0 C in THF and
gave allylic alcohols 17 9 and 180 in very good yields. No
products from the 1,4 addition of the organolithium were
observed. The second series of allylic oxidations with PDC
did not proceed as smoothly, but gave unsaturated ketones 182
and 183 in reasonable yields. The alcohol-directed
epoxidation of the allylic alcohols was not attempted because
in a similar case that we had tried it was found that the
other olefin was sometimes epoxidized. So the epoxidation of
the unsaturated ketones was attempted by using a 30% aq.
hydrogen peroxide solution and K2CO3 as the base. This
protocol prepared the desired starting materials with overall
yields of 24% for 185 (R=H, 2 steps), 49% for 186 (R=Me, 4
steps), 33% for 187 (R=n-Bu, 4 steps).
In a typical cyclization, the epoxy ketone was dissolved
in benzene (0.5 M) then 2.5 eqs. of TBTH, and 0.1 eq. of
AIBN were added. This mixture was degassed with argon for 20
minutes, then the reaction was heated to 85 C (bath temp.).
The reactions were monitored by TLC, and in most cases the
starting material was consumed within a few hours. These
reactions were run at higher concentrations because at first
it seemed that the epoxide's opening may have been sluggish,
but epoxide openings were also' achieved at low
concentrations, such as 0.025 M for 185.


62
The conditions that the reactions were run at and the
ratio of products are shown in Scheme 3-10. The precursor
was used several times because it was easily accessible from
commercially available materials. However, the drawback to
this precursor was that the products which were formed were
generally a mixture of isomers due to four appendages on the
products. This mixture was not easily separated, and a
thorough identification of stereochemistry was not considered
possible. In general, it was believed that there were only
two isomers formed. This was less then might be expected
with three different chiral centers in the product, which
could give rise to four different diastereomers.
Substrate
186 (R=Me)
187 (R=nBu)
Conditions
0.5 M, 2.5 eq TBTH
0.5 M, 2.5 eq TBTH
Major;Minor (% Yield)
189:190
3:2 (83% Yield)
191:192
1:1 (81% Yield)
Scheme 3-10


63
The proposed mechanism at this point is shown in Scheme
3-11 for the methyl example. We believed that the products
shown in Scheme 3-10 were a result of the proficient ability
of alkoxy radicals to abstract hydrogens, such as in 194.
This would generate allylic-stabilized radical 195 which also
can be represented as resonance form 19 6. The 5-hexenyl
cyclization appeared to proceed smoothly yielding 197, which,
after additional reactions with TBTH and a proton source,
would yield the products shown in Scheme 3-10.
Scheme 3-11


64
For this mechanism to be operative there needed to be
hydrogens on the group which was attached to the ketone, as
in 194 in Scheme 3-11. If there were no hydrogens, then
radical 195 could never be generated. Compound 185 possessed
no abstractable hydrogens, and so its cyclization, or
inability to cyclize, would be a key test for this proposed
mechanism. When this reaction (Scheme 3-12) was carried out
we were surprised to find that 185 cyclized efficiently to
afford cyclopentanols.
Substrate
185 (R=H)
Conditions
0.1 M, 2.0 eg TBTH
Scheme 3-12
Major;Minor (% Yield)
198:199
3:1 (81% Yield)
At this point we realized the original mechanism that
was proposed (Scheme 3-11) was not possible. After careful
examination of the literature, the references to 1,5-tin
transfer (Scheme 3-7) were found,76b' 83,84 which at first


65
seemed to be a bit obscure, but in time we realized that this
was indeed the operative mechanism. The proposed mechanism,
now revised as it applies to the cyclization of 18 5f is shown
in Scheme 3-13.
H
H
Bu3Sn
185
H
Scheme 3-13
The deciding factor between these mechanisms was the
geometry of the olefin which was produced when the epoxide
was fragmented (Figure 3-2) If the alkoxy radical and the
tin enolate are cis to one another, as in 2 0 9. then 1,5-
migration can occur;
but,
if they are trans
then the


66
migration cannot occur. If a ketone bears a group with a
hydrogens then the alkoxy radical in 210 could abstract them
and the reaction could proceed by the mechanism in Scheme 3-
11.
OSnBu3
H
Figure 3-2
Transition states model of cis and trans tin enolate
So the dilemma we were faced with was that there were
two possible mechanisms which the reactions discussed in this
chapter could follow. The initial reactions in Scheme 3-10
could go by either mechanism, while the reactions in Scheme
3-12 most likely followed the 1,5-tin transfer mechanism.
The tin transfer mechanism must proceed through transition
state 207 which is more sterically congested. We believe
that a weak chelation effect between the tin enolate and the


67
resulting alkoxy radical would help overcome any steric
problems. This six-membered ring chelate would eventually
develop into the transition state for the 1,5-tin transfer.
A new system was devised which would illuminate the reaction
pathway of the initial reactions in Scheme 3-10. The
synthesis of this compound is shown in Scheme 3-14.
O
211
1.DIBAL,CH2C12
-78C
2.VinylMgBr,THF
0C
51% Yield
Scheme 3-14


68
The low temperature reduction of e-caprolactone with
DIBAL produced a product which seemed to polymerize rapidly,
and was not characterized. Instead, after a crude
purification, it was treated with vinyl magnesium bromide
which yielded diol 212 in 51% yield for the two step
reaction. This diol was then epoxidized using mCPBA to give
a very polar product which was extremely hard to
chromatograph. PDC oxidation of diol 213 did not produce a
large amount of the desired product. This might have been
because the highly polar substrate was difficult to separate
from the PDC. The highly touted Dess-Martin Periodinane87 was
synthesized, and 2 eqs. of it was used for the oxidation
which proceeded smoothly to produce 214 in a 68% yield. The
final product was synthesized by a stabilized Wittig reaction
on the aldehyde to give 215 in 10% overall yield in five
steps from caprolactone.
The reason the cyclization of 215 was important was
because it could help provide additional information about
whether the hydrogen abstraction mechanism is valid for these
fragmentations. If this cyclization succeeded in producing
cyclopentanes, then the alkoxy radical must be abstracting a
hydrogen; if it does not succeed, then the 1,5-tin transfer
mechanism must be valid. The starting material was dissolved
in benzene (0.01 M), then 1.5 eqs of TBTH and 0.1 eq. of AIBN
were added. The reaction was degassed with argon and the
reaction was refluxed. The only product which was isolated


69
was the opened epoxide 216. No cyclized products could be
isolated.
TBTH,AIBN
C6H6,A
70%
Scheme 3-15
This suggested that the mechanism in Scheme 3-10, or the
hydrogen abstraction mechanism, was a less-likely
possibility. We felt that hydrogen abstraction by the alkoxy
radical would generate a 5-hexenyl radical which would likely
cyclize onto the activated olefin. It should be noted that
hydrogen abstraction may have actually occurred but the
ketone stabilized radical was electron poor and could not add
to the LUMO of the alkene The probable mechanism which can
now be proposed is the 1,5-tin transfer which was originally
proposed by Davies.84 When this tin transfer occurred in the
reaction of 215 a radical was generated a to the ketone, but
too far away to cyclize with the activated olefin, and it was
simply quenched with TBTH to give the final product.
In conclusion, the work which is presented in this
chapter has shown that the fragmentation of epoxy ketones
proceeds by a relatively novel 1,5-tin transfer. The
products of these reactions are highly functionalized
cyclopentanols Although the stereochemistry of this


70
cyclization could be improved, the number of isomers isolated
was far less then might be expected from such a densely
functionalized molecule. In this regard, radical
cyclizations were conducted on 186 and 187 with Sml2 and the
same products as mentioned above were isolated. However,
initial TLC showed that a much higher degree of
stereoselection (around 10:1) was possible. But the ketone
center turned out to be very epimerizable, and these
selectivities were never realized. Future work in this
direction could potentially yield a very a fruitful study.


CHAPTER 4
SUMMARY
The studies described in this dissertation are an
attempt to expand the realm of free-radical chemistry. Free-
radical methodology has been dominated by halogen and group
abstraction as the source of organic radicals. Although,
these methods have helped establish free-radical reactions as
a valuable tool in the synthesis of complex molecules,
hopefully, this thesis will show that there are quality
alternatives to these methods. The mild reaction conditions,
and the ability to control reactivity, stereoselectivity, and
regioselectivity in these reactions are certainly different
qualities from the original "unruly" reputation of free
radicals 40 years ago.
A problem associated with "classical" radical chemistry
is illustrated by the work of Dennis Curran shown in Scheme
1-1. In his synthesis of hirsutene, Curran took a molecule
which had three exploitable functional groups (1) and
produced a molecule which had only functional group (2.) The
use of free-radical cyclizations on this molecule had
virtually stripped it of usable functionality. Although, the
loss of functionality was intended in the case of hirsutene,
it still demonstrates that sometimes radical cyclizations
71


72
result in compounds which can not be further functionalized.
A goal of this thesis was to show that radical cyclizations
could be conducted successfully with carbonyls as free-
radical precursors.
In the first study, TBTH was used to couple the p-
carbons of a,(3-unsaturated ketones and activated olefins to
produce highly functionalized cyclopentanes. This study
revealed that unsaturated ketones were very effective at
delocalizing the radical away from the tin ketyl which was
formed when tributyltin radical added to the ketone.
Unactivated alkenes did not undergo cyclization reactions,
but instead underwent simple reduction of the unsaturated
ketone. Activated alkenes that were tethered to this 0-
stannyl allylic radical participated in 5-hexenyl radical
cyclizations to form cyclopentanes. Excellent anti
stereoselectivities were achieved (>50:1) when these
cyclizations were conducted at low concentrations. The
effect of concentration on the product ratios seemed to
indicate that these cyclizations were an artifact of a
reversible cyclization. These observations are in direct
contrast to how an a,P~unsaturated ketone is normally viewed
in free radical reactions. These studies show that for the
first time that unsaturated ketones can serve as radical
precursors in a reagent-based study.
This study also demonstrated that the anionio character
of the tin ketyl can be trapped by electrophilic reagents.
All of the activating groups on the alkenes reacted with the


73
tin enolate in a second cyclization when both appendages were
syn to the newly formed cyclopentane. When the appendages
were anti to one another, ring strain would not allow them to
react, but electrophilic reagents such as bromine and
deuterium oxide were able to trap this anti intermediate.
This is important because the sequencing of one- and two-
electron reactions is rapidly emerging as an important
synthetic tool.87
Chapter 2 also demonstrated that the intermolecular
coupling of a,(3-unsaturated ketones was possible. Although
this methodology appeared very limited to substrates bearing
phenyl or radical-stabilizing groups, the implementation of
either syringe pump or hydrideless tin techniques to these
reactions may expand the applicability of this reaction.
The third chapter examined the reactions of epoxy
ketones. The original goal of synthesizing tetrahydrofurans
by this methodology was never realized. The well-known
ability of alkoxy radicals to abstract hydrogen from adjacent
carbons was not the problem with this project. It was a
little-known 1,5-tin transfer mechanism which kept the alkoxy
radical from cyclizing onto adjacent olefins. However, the
carbon-centered radical, which was produced by this tin
transfer, underwent cyclization reactions with tethered
olefins. The product of these cyclizations were highly
substituted cyclopentanols.
Collectively, these studies show that carbonyls can be
effectively utilized as free-radical precursors. Hopefully


74
this work will begin to establish the use of ketones and
aldehydes in that regard. The cyclizations of unsaturated
ketones and epoxy carbonyls have shown that these systems can
offer excellent stereoselectivities along with a greater
degree of manipulatable functionality. These cyclizations
are well suited towards the synthesis of complex, and highly
functionalized cyclopentanes, similar to those found in
natural products. They will hopefully become a new and
effective weapon in the arsenal of synthetic chemists.


75
CHAPTER 5
EXPERIMENTAL SECTION
General
Melting points were determined on a Thomas-Hoover
capillary melting point apparatus and are uncorrected.
Infrared spectra were recorded on a Perkin-Elmer 283B FTIR
spectrophotometer and are reported in wave numbers (cm-1) 1H
Nuclear magnetic resonance (NMR) spectra were recorded on a
Varian VXR-300 (300 MHz) spectrometer, and General Electric
QE-300 (300 MHz). 13C NMR spectra were recorded at 75 MHz on
the above mentioned spectrophotometers. Chemical shifts are
reported in ppm downfield relative to tetramethylsilane
( (CH3)4S) as an internal standard in CDCI3. Mass spectra and
exact mass measurements were performed on Finnigan MAT95Q,
Finnigan 4515, or Finnigan ITD mass spectrometers. Elemental
analysis was performed by Atlantic Microlab, Inc., Norcross,
GA 30091.
All reactions were run under an inert atmosphere of
argon using flame or heat dried apparatus. All reactions
were monitored by thin layer chromatography (TLC) and judged
complete when starting material was no longer visible in the
reaction mixture. All yields reported refer to isolated
material judged to be homogeneous by thin layer


76
chromatography and NMR spectroscopy. Temperatures above and
below ambient temperature refer to bath temperatures unless
otherwise stated. Solvents and anhydrous liquid reagents
were dried according to established procedures by
distillation under nitrogen from an appropriate drying agent:
ether, benzene, and THF from benzophenone ketyl; CH2CI2 from
CaH2 Other solvents were used "as received" from the
manufacturer.
Analytical TLC was performed using Kieselgel 60 F-254
precoated silica gel plates (0.25 mm) using phosphomolybdic
acid in ethanol as an indicator. Column chromatography was
performed using Kieselgel silica gel 60 (230-400 mesh) by
standard flash89 and suction chromatographic techniques.
All GC experiments were performed on a Varian 3500
capillary gas chromatogarph using a J & W fused silica
capillary column (DB5-30W; film thickness 0.25 [1) .
Experimental Procedures and Results
(3E.8Z)-Tetradecadien-2-one (1Q1)
To a previously dried 25 ml round bottom flask (RBF) was
added methyl ketone Wittig reagent (1.70 g, 5.31 mmol) along
with a magnetic stirrer. 5-Undecenal90 (0.40 g, 2.38mmol) was
weighed into a separate flask and transferred with 2.6 ml of
CHCI3. Reaction was quenched with water and extracted with
Et20. The Et£0 layer was washed with sat. brine soln., dried


77
over Na2SC>4, and concentrated in vacuo. The concentrate was
purified by flash chromatography on a silica gel column to
yield a clear oil (0.40 g, 81.0%): Rf 0.75 (70% Et20/hexane);
300 MHz XH NMR (CDC13) 5 6.81 (1H, m) 6.08 (1H, d, J=16 Hz),
5.38 (2H, m) 2.26 <3H, s), 2.24 (2H, m), 2.03 (4H, m) 1.54
(2H, m) 1.30 (6H, m) 0.89 (3H, t, J=7 Hz); 75 MHz 13C NMR
(CDC13) 5 198.58, 148.23, 131.45, 131.01, 128.61, 32.58,
32.01, 31.56, 29.41, 28.18, 27.29, 26.29, 22.60, 14.08; IR
(neat) 3006, 1700, 1628, 1459, 1253, 977 cm-1; MS (Cl), m/e
(relative intensity) 209(m++l, 9), 150(20), 137(21), 97(35),
95 (28), 84 (25), 81 (34), 69 (28), 67 (29), 43 (100); HR MS (Cl)
209.1910 (calc, for C14H25O: 209.1905).
7-Oxo-5-octenal (10 4)91
Glutaric dialdehyde (100 ml of a 50% aq. solution, 552.3
mmol) was placed into a 300 ml RBF along with a magnetic
stirrer. The methyl ketone Wittig reagent (25.5 g, 80.1
mmol) was dissolved in CH2CI2 (100 ml) and placed into a large
addition funnel. CH2CI2 (50 ml) was added to the dialdehyde
in the reaction flask and the ylide solution was slowly added
to the reaction mixture. The addition of the ylide took
about 1.5 hours, and the funnel was rinsed with 10 ml of
CH2CI2- The reaction was allowed to proceed overnight and was
extracted with H2O (2 x 100 ml). The organic layer was dried
with Na2S04 and concentrated in vacuo. Column chromatography
of the residue produced a colorless oil (8.2784 g, 59.0 mmol,
74% yield): Rf 0.40 (70% Et2/hexane); 300 MHz 1H NMR (CDCI3)


78
5 9.79 (1H, s), 6.77 (1H, dt, J=16.0, 6.9 Hz), 6.09 (1H, d,
J=16.0 Hz), 2.52 (2H, t, J=6.9 Hz), 2.28 (5H, m) 1.84 (2H,
m); 75 MHz 13C NMR (CDC13) 5 201.51, 198.31, 146.65, 131.87,
42.98, 31.56, 26.95, 20.38.
General Procedure for Preparation of Activated Olefins
To a previously dried flask was added the appropriate
stabilized ylide (7 mmol) and a magnetic stir bar. CHC13
(3.5 ml) was then added and the reaction was stirred. Once
the ylide was completely dissolved, 7-oxo-5-octenal 104 (3.5
mmol) was added. Reaction was followed by TLC and starting
material was usually consumed in 1-2 days. The reaction
mixture was concentrated in vacuo, and this residue was flash
chromatographed to yield the activated olefin.
9-0XO-2E.7E-decadienenitrile (105)
Yield (47%); Rf 0.55 (90% Et20/hexane) ; 300 MHz 1H NMR
(CDCI3) 5 6.75 (2H, m) 6.09 (1H, dt, J=16.0, 1.4 Hz), 5.38
(1H, dt, J=16.0, 1.4), 2.27 (7H, m), 1.68 (2H, m); 75 MHz 13C
NMR (CDCI3) 6 198.24, 154.81, 146.36, 131.93, 117.28, 100.55,
32.60, 31.51, 27.06, 26.08; IR (neat) 2933, 2863, 2222 (s) ,
1731, 1696, 1673, 1631, 1363, 1256, 976 cm"1; MS (El), m/e
(relative intensity) 164(M++1, self Cl,18), 148(35), 55(54),
43(100), 41(33), 39(37); HR MS (El) 163.09857 (calc, for
c10h13NO: 163-09971) .


79
3E.8E-Undecadiene-2.10-dione (106)
Yield (52%); Rf 0.55 (50% EtOAc/hexane); 300 MHz 1H NMR
(CDC13) 5 6.78 (2H, dt, J=16.0, 7.5 Hz), 6.04 (2H, d, J=16.0
Hz), 2.37 (10H, m) 1.67 (2H, m) ; 75 MHz 13C NMR (CDC13) 5
198.27, 146.77, 131.78, 31.73, 27.02, 26.51; IR (neat) 2932,
1697, 1673, 1626, 1428, 1363, 1255, 1185, 977, 607 cm"1; MS
(El), m/e (relative intensity) 180(M+, 1), 137(43), 81(23),
43 (100); HR MS (El) 180.1151 (calc, for CnH1602: 180.11503).
Methyl-3 -OXO-2E.7E-decadienoate (107)
Yield (49%); Rf 0.40 (70% Et20/hexane); 300 MHz 1H NMR
(CDC13)
5 6.95
(1H,
dt, J=16.0,
6.9 Hz),
6.78
(1H,
dt,
J=16.0
6.9 Hz)
, 6.08
(1H,
dt, J=16.0,
1.5 Hz),
5.84
(1H,
dt,
J=16.0
1.5 Hz), 3.73 (3H,s), 2.24 (7H, m) 1.67 (2H, m); 75 MHz 13C
NMR (CDCI3) 8 198.29, 166.78, 148.13, 146.90, 131.63, 121.53,
51.34, 31.57, 31.38, 26.87, 26.28; IR (neat) 1723, 1697,
1674, 1627, 1436, 1362, 1272, 1256, 1202, 977 cm-1; MS (El),
m/e (relative intensity) 197(M++l, self Cl, 82), 196 (M+, 2),
165(80), 164(31), 137(75), 136(55), 121(42), 93(61), 81(89),
79(28), 68(32), 55(51), 53(52), 43(100), 41(41), 39(56); HR
MS (El) 196.10913 (calc, for C11H1603: 196.10995).
General Procedure for Radical Cyclization of Olefins
A round bottom flask and a condenser were flame dried
and allowed to cool under a argon atmosphere. After the
flask had cooled, the activated olefin (0.5 mmol) was weighed


80
into the flask. Then AIBN (0.05 mmol), followed by TBTH (1.5
mmol) and freshly distilled benzene (5 ml) were syringed into
the flask. This solution was carefully degassed for 15 min
with argon. Then the reaction was warmed to 85C until the
reaction was complete by TLC. When no starting material was
observed by TLC, the reaction mixture was concentrated in
vacuo, and the mixture was separated by flash chromatography
to give the cis and trans cyclized products.
8Z-Tetradecen-2-one (102)
Yield
(90%); Rf 0
.77 (70% Et2<0/hexane) ;
300
MHz 1H
NMR
(CDCI3) 5
5.38(2H, m) ,
2.42 (2H, t, J=8 Hz),
2 .
14 (3H,
s) ,
1.97 (4H,
m) 1.58 (2H,
m) 1.30 (10H, m) 0.
89
(3H, t,
r-
II
Hz); 75 MHz 13C NMR (CDC13) 5 209.0, 130.6, 129.9, 43.7, 32.3,
31.3, 29.4, 29.3, 28.8, 27.29, 26.9, 23.6, 22.5, 14.0; IR
(neat) 2926, 2855, 1719, 1462, 1358, 1286, 1161, 1075, 968,
723 cm-1; MS (Cl), m/e (relative intensity) 211(m++l, 92.7),
193(32), 125(22), 85(41), 43(100); Anal. Ci4H260: 79.82% C,
12.40% H (calc. 79.94% C, 12.46% H) .
trans- (2- (2-Qxopropyl) cyclooentyl) ethanenitrile (1Q8.L
Yield (71%); Rf 0.60 (90% Et20/hexane); 300 MHz 1H NMR
(CDCI3) 5 2.7-2.3 (4H, m) 2.14 (3H, s), 1.98 (3H, m) 1.77
(1H, m), 1.55 (2H, m), 1.44 (1H, m), 1.13 (1H, m); 75 MHz 13C
NMR (CDCI3) 6 207.89, 119.15, 48.75 ,41.87, 40.28, 32.66,'
32.06, 30.23, 23.55, 21.96; IR (neat) 2954, 2872, 2244 (s),
1713, 1452, 1424, 1359, 1294, 1227, 1174 cm"1; MS (El), m/e


81
(relative intensity) 166(M++1, self Cl, 20), 81(24), 58(36),
43(100), 34(48); HR MS (El) 165.11593 (calc, for C10H15NO:
165.11536).
cis-2-AcetYl-3-iminobicycloT33.01 octane (10 9)
Yield (24%); Rf 0.40 (90% Et20/hexane); 300 MHz 1H NMR
(CDC13) 5 3.37 (1H, m) 2.70 (2H, m) 2.23 (1H, m) 2.10 (3H,
s), 1.88 (1H, m) 1.74 (1H, m) 1.53 (4H, m) 1.36 (1H, m) ,
1.24 (1H, br s); 75 MHz 13C NMR (CDC13) 5 196.19, 162.76,
110.90, 48.31, 41.29, 38.22, 34.87, 34.83, 27.95, 25.81; IR
(KBr) 3355, 2929, 2856, 1627, 1498, 1340, 1316, 1284, 1270,
926 cm-1; MS (El), m/e (relative intensity) 165(M+, 29),
136(100), 43(30), 34(52); HR MS (El) 165.11526 (calc, for
c10h15NO: 165.11536).
trans-1-(2-(2-Oxopropyl)cyclopentyl)-2-propanone (110)
Yield (73%); Rf 0.70 (50% EtOAc/hexane); 300 MHz 1H NMR
(CDCI3) 5 2.60 (2H, dd, J=18, 5 Hz), 2.36 (2H, dd, J=18, 9
Hz), 2.14 (6H, s), 1.89 (4H, m), 1.58 (2H, m) 1.25 (2H, m) ;
75 MHz 13C NMR (CDCI3) 5 208.68, 48.97, 40.93, 32.35, 30.26,
23.50; IR (neat) 3602, 2949, 2871, 1713, 1407, 1359, 1274,
1230, 1176, 1154 cm-1; MS (El), m/e (relative intensity)
183(M++1, self Cl,100), 125(25), 124(45), 81(32), 43(95); HR
MS (El, self Cl) 183.13866 (calc, for C1;LH1902: 183.13851).


82
cis-2(R)-Acetvl-3(S)-hvdroxv-3-methYlbicyclo T3.3.01 octane (111)
Rf 0.65 (50% EtOAc/hexane) ; 300 MHz XH NMR (CDC13) 5
4 .
09
(1H,
br
s), 2.86-2.
.67 (1H, d, J=9.3
Hz) ,
2.23
(3H, s)
2.
00
(1H,
dd,
J=7.8, 13,
.2 Hz), 1.80-1.55
(6H,
m) ,
1.31 (3H
s)
r
1.13
(1H,
dd, 9.3,
13.2 Hz); 75 MHz
13C
NMR
(CDCI3) 1
214.64, 82.81, 66.34, 48.28, 47.68, 42.04, 33.26, 32.84,
32.15, 26.21, 25.63; IR (neat) 3474 (br), 2943, 2862, 1689,
1453, 1372, 1237, 1176, 1138, 934 cm"1; MS (El), m/e (relative
intensity) 182(m+, 0.1), 167(1), 124(71), 81(10), 66(20),
43(100); HR MS (Cl) 183.1381 (calc, for CnH1902: 183.1385).
trans-Methyl(2-(2-oxopropvl)cvclopentyl)ethanoate (112)
Yield (58%); Rf 0.45 (70% Et20/hexane) ; 300 MHz 1H NMR
(CDC13) 8 3.67 (3H, s), 2.65-2.17 (4H, m), 2.14 (3H, s), 1.89
(4H, m) 1.59 (2H, m), 1.23 (2H, m); 75 MHz 13C NMR (CDC13) 5
208.66, 173.66, 51.46, 48.91, 42.01, 40.76, 39.04, 32.33,
32.10, 30.27, 23.44; IR (neat) 2952, 2872, 1738, 1716, 1436,
1359, 1258, 1194, 1176, 1155 cm-1; MS (Cl), m/e (relative
intensity) 199(M++1, 63), 167(92), 141(27), 81(60), 67(37),
43(100); HR MS (El) 167.10746 (calc, for C11H1603 -OCH3:
167.10721).
cis-2-Acetyl-3-oxobicyclo f 3.3.01 octane (113)
Yield (27%); Rf 0.65 (70% Et20/hexane); 300 MHz XH NMR
(CDCI3) 8 13.8 (1H, br s) 3.26 (1H, m), 2.70 (2H, m) 2.06
(3H, s), 1.92 (3H, m), 1.58 (2H, m), 1.45 (2H, m) ; 75 MHz 13C


83
NMR (CDCI3) 5 202, 180.39, 115.27, 43.43, 42.93, 37.16, 34.80,
34.39, 26.04, 21.44; IR (neat) 2948, 2864, 1710, 1652, 1448,
1389, 1286, 1235,
937,
893
cm 1; MS
(El)
, m/e (relative
intensity) 166(M+,
76) ,
137(100), 124(30),
95 (48), 43 (98),
41(31), 39(32); HR
MS
(El)
166.09905
(calc, for C10H14O2
166.09938).
General Procedure for Enolate Trapping Studies
A round bottom flask and a condenser were flame dried
and allowed to cool under a argon atmosphere. After the
flask had cooled, activated olefin 107 (0..250 mmol) was
weighed into the flask. Then AIBN (0.025 mmol), followed by
TBTH (0.265 mmol) and freshly distilled benzene (25 ml) were
syringed into the flask. This solution was carefully
degassed for 15 min with argon. The reaction was warmed to
85C for one hour, then either D20 (XS) or Br2 in CC14
(.750mmol) was added. When no starting material was observed
on TLC, the reaction mixture was concentrated in vacuo, and
the mixture was separated by flash chromatography to give
mostly trans cyclized products.
Methyl(2-(l-bromo-2-oxopropyl)cyclopentyl)ethanoate (126)
Yield (86%); Rf 0.68 (90% Et20/hexane); 300 MHz 1H NMR
(CDCI3) 5 4.45 (1H, d, J=7.5 Hz), 3.68 (3H, s), 2.47 (1H, dd,
J=7.5, 15 Hz), 2.38 (3H, s), 2.27 (1H, dd, J=9, 15 Hz), 2.3-
2.1 (2H, m), 1.90 (2H, m), 1.63 (2H, m), 1.45-1.2 (2H, m); 75
MHz 13C NMR (CDCI3) 8 201.96, 173.09, 60.27, 51.48, 46.41,


84
40.02, 38.98, 32.65, 30.16, 27.48, 23.81; IR (neat) 2953,
2871, 1736, 1436, 1358, 1257, 1198, 1166, 1086, 1014 cm"1; MS
(El), m/e (relative intensity) 278(m+, 81Br,-), 276(m+, 79Br,~
), 165(11), 141(16), 123(15), 95(17), 81(18), 43(100); HR MS
(Cl) 279.0417 (calc, for C11H1881Br03: 279.0419).
Methyl(2-(l-deutero-2-oxopropyl)cyclopentyl)ethanoate (127)
Yield (87%),
85% Deuterium
incorporation; Rf
0.60
(90%
Et20/hexane); 300
MHz 7H NMR
(CDC13) 8 3.67 (3H,
s) ,
2.62
(0.6H, dd, J=6,
18 Hz), 2.46
(1H, dd, J=6, 15
Hz) ,
2.35
(0.5H, dd, J=9, 18 Hz), 2.21 (1H, dd, J=9, 15 Hz), 2.14 (3H,
s), 1.89 (4H, m) 1.59 (2H, m) 1.23 (2H, m) ; MS (Cl), m/e
(relative intensity) 200(m+, 25), 199(24), 168(100), 167(99),
149 (3), 140(12), 139(9), 121(4).
Hydrodimerization of Chalcone
Chalcone 132 (0.2057 g, 0.9877 mmol) was weighed into a
previously dried 5 ml RBF. Freshly distilled Benzene (1 ml),
a magnetic stir bar, AIBN (7.0 mg, 0.04 mmol), and TBTH (0.15
ml, 0.5577 mmol) were added and the reaction was degassed for
15 min. After TLC showed that chalcone was consumed, the
reaction was concentrated in vacuo, and the residue was
separated by column chromatography. The simple reduced
product, 1,3-diphenyl-1-propanone,92 133 was obtained as a
colorless solid which melted at 69-70C (lit. 70-72C). The
hydrodimerized and cyclized product,72 134 was obtained as a


85
mixture of isomers which was a colorless solid which melted
at 93-101C (lit. 91-99C).
4.8-Dimethvl-3.7-nonadiene-2-ol (179)93
Geranial (mixture of citral and neral) (2.0327 g, 13.353
mmol) was weighed into a 50 ml RBF, then THF (25 ml) was
added. The temperature was lowered to 0C and 1.5M MeLi
(13.5 ml, 20.25 mmol) was syringed into the reaction mixture.
After an hour, the reaction was quenched with a sat. NH4CI
soln., and then extracted with Et20 (3 x 25 ml). The ether
layer was dried over Na2SC>4 and concentrated to give a
colorless oil (2.1418 g, 12.728 mmol, 95.3% yield) which was
a mixture of cis and trans double bond (spectra reported for
major peaks of mixture): 300 MHz 1H NMR (CDCI3) 5 5.22 (1H, d,
J=9
Hz) ,
5.09 (1H, t,
J=7 Hz), 4
.57
(1H, m) ,
2.08
(2H,
m) ,
2.00
(2H,
t, J=7 Hz),
1.88 (1H,
br
s), 1.69
(6H,
s) ,
1.60
(3H,
s) ,
1.22 (3H, d,
J=8 Hz);
75
MHz 13C
NMR
(CDC1
3) &
137.23, 130.23, 129.17, 123.90, 64.64, 39.39, 26.35, 25.58,
23.55, 17.60, 16.33.
7.ll-Dimethyl-6.10-dodecadiene-5-ol (180)94
Geranial (mixture of citral and neral) (1.9955 g, 13.108
mmol) was weighed into a 50 ml RBF, then THF (25 ml) was
added. The temperature was lowered to 0C and 2.5M BuLi (7.9
ml, 19.75mmol) was syringed into the reaction mixture. After
an hour, the reaction was quenched with a sat. NH4CI soln.,
and then extracted with Et20 (3 x 25 ml) The ether layer


86
was dried over Na2SC>4 and concentrated to give a colorless oil
(2.65418 g, 12.617 mmol, 96.3% yield) which was a mixture of
cis and trans double bond (spectra reported for major peaks
of mixture): 300 MHz XH NMR (CDC13) 8 5.22-5.04 (2H, m), 4.33
(1H, m) 2.08 (5H, m) 1.69 (6H, s), 1.61 <3H, s), 1.31 (6H,
m) 0.90 (3H, t, J=7 Hz); 75 MHz 13C NMR (CDC13) 8 138.12,
131.53, 128.16, 123.92, 68.56, 39.53, 37.41, 27.58, 26.33,
25.60, 22.68, 17.62, 16.51, 14.02.
4.8-Dimethyl-3F 7-nonadiene-2-one (182)93
Allylic alcohol 179 (2.1418 g, 12.728 mmol) was weighed
into a 100 ml RBF with PDC (9.6 g, 25 mmol), CH2CI2 (25 ml),
and crushed 4 molecular sieves.95 The next day the reaction
was diluted with Et20 (75 ml) and this soln. was allowed to
stir for four hours. Suction chromatography was used to
separate the bulk of the PDC, and sieves. The eluent wss
concentrated and purified by column chromatography to give a
colorless oil (1.5105 g, 9.085 mmol, 71.4% yield) which was a
mixture of cis and trans double bond (spectra reported for
major peaks of mixture) : 300 MHz *H NMR (CDC13) 8 6.08 (1H,
s), 5.09 (1H, m), 2.16 (10H, m), 1.71 (3H, s), 1.62 (3H, s);
75 MHz 13C NMR (CDC13) 8 198.59, 158.15, 132.35, 123.54,
122.96, 41.11, 31.65, 26.08, 25.57, 19.18, 17.59.
7.1l-Dimethvl-6.10-dodecadiene-5-one (183)96
Allylic alcohol 180 (2.6541 g, 12.617 mmol) was weighed
into a 100 ml RBF with PDC (9.5 g, 25 mmol), CH2CI2 (25 ml),


87
and crushed 4 molecular sieves95. The next day the reaction
was diluted with Et2 (75 ml) and this soln. was allowed to
stir for four hours. Suction chromatography was used to
separate the bulk of the PDC, and sieves. The eluent was
concentrated and purified by column chromatography to give a
colorless oil (1.0289 g, 4.939 mmol, 39.1% yield) which is a
mixture of cis and trans double bond (spectra reported for
major peaks of mixture): 300 MHz 1H NMR (CDCI3) 5 6.05 (1H,
s), 5.08 (1H, t, J=7.2 Hz), 2.60 (2H, t, J=8.1 Hz), 2.42 (2H,
m) 2.14 (5H, m) 1.69 (3H, s) 1.62 (3H, s), 1.56 (2H, m) ,
1.33 (2H, m), 0.91 (3H, t, J=7,2 Hz); 75 MHz 13C NMR (CDC13) 8
201.43, 157.77, 132.34, 123.88, 123.20, 44.11, 41.15, 33.74,
26.10, 25.60, 22.37, 19.23, 17.62, 13.86; IR (neat) 2960,
2930, 2873, 1688, 1619, 1450, 1377, 1131, 1076, 1040 cm"1; MS
(El), m/e (relative intensity) 208(m+,7), 166(22), 165(21),
151 (70), 123 (46), 98(41), 85(31), 83 (100), 82(17), 69(38),
57 (18), 55 (17); HR MS (El) 208.1856 (calc, for C14H24O :
208.1827).
3.7-Dimethyl-2.3-epoxv-7-octenal (185)
Unsaturated aldehyde 178 (0.9895 g, 6.500 mmol), MeOH
(12 ml), 30% H2O2 in water (1.4 ml, 13.7 mmol), and a sat. aq.
soln. of K2CO3 (2.9 ml) were added to a 25 ml RBF. The next
day the reaction was quenched with sat. NaHCC>3. This soln.
was extracted with Et20 (3 x 25 ml), then the ether layer was
dried over Na2SC>4 and concentrated in vacuo. Column
chromatography of the residue produced a colorless oil (0.291


88
g, 1.73 mmol, 26.6% yield): Rf 0.62 (50% Et20/Hexane); 300
MHz XH NMR (CDC13) 5 9.43 (1H, d, J=6 Hz), 5.07 (1H, t, J=7
Hz), 3.14 (1H, d, J=6 Hz), 2.12 (2H, m) 1.9-1.5 (11H, m); 75
MHz 13C NMR (CDCI3) 5 198.65, 132.54, 122.58, 64.39, 63.41,
38.18, 33.28, 25.51, 21.98, 17.06; IR (neat) 2970, 2928,
2858, 1723, 1674, 1452, 1409, 1383, 1110, 800 cm"1; MS (Cl),
m/e (relative intensity) 169(m++l,33), 151(72), 137(57),
135(25), 123(100), 111(17), 109(66), 95(16), 82(15), 81(17);
HR MS (Cl) 169.1228 (calc, for C10H17O2: 169.1226).
4,8-Dimethy1-3.4-epoxy-7-nonene-2-one (186)
Unsaturated ketone 182 (1.5105 g, 9.0851 mmol), MeOH (16
ml), 30% H2O2 in water (2.0 ml, 19.6 mmol), and a sat. aq.
soln. of K2CO3 (3.3 ml) were added to a 25 ml RBF. The next
day the reaction was quenched with sat. NaHCC>3. The reaction
mixture was extracted with Et20 (3 x 25 ml), then the ether
layer was dried over Na2SC>4 and concentrated in vacuo. Column
chromatography of the residue produced a colorless oil
(1.3225 g, 7.256 mmol, 79.9% yield): Rf 0.54 (50%
Et20/hexane) ; 300 MHz *H NMR (CDC13) 5 5.11 (1H, t, J=7 Hz),
3.43 (1H, s), 2.21 (3H, s), 2.13 (2H, m), 1.85-1.50 (8H, m),
1.25 (3H, s); 75 MHz 13C NMR (CDC13) 5 204.05, 132.36, 122.84,
64.74, 63.11, 38.06, 32.19, 27.80, 25.58, 23.60, 16.00; IR
(neat) 2970, 2922, 1723, 1452, 1404, 1382, 1356, 1241, 1187,
1079 cm-1; MS (Cl), m/e (relative intensity) 183(m++1,11) ,
181(100), 165(24), 163(17), 143(47), 139(40), 137(10),


89
125(36), 123(11), 121(28); HR MS (Cl) 183.1361 (calc, for
C11H19O2 : 183.1385) .
7,ll-Dimethyl-6.7-epoxy-10-dodecene-5-one (187)
Unsaturated ketone 183 (0.9697 g, 4.654 mmol), MeOH (8
ml), 30% H2O2 in water (1.0 ml, 9.8 mmol), and a sat. aq.
soln. of K2CO3 (1.8 ml) were added to a 25 ml RBF. The next
day the reaction was quenched with sat. NaHCC>3. The reaction
mixture was extracted with Et20 (3 x 25 ml), then the ether
layer was dried over Na2SC>4 and concentrated in vacuo. Column
chromatography of the residue produced a colorless oil
(1.0176 g, 4.535 mmol, 97.5% yield): Rf 0.70 (50%
Et20/hexane) ; 300 MHz XH NMR (CDC13) 5 5.11 (1H, t, J=7 Hz),
3.43 (1H, s), 2.50 (2H, m), 2.02 (2H, m), 1.87-1.47 (10H, m),
1.35 (2H, m) 1.22 (3H, s), 0.91 (3H, t, J+7 Hz); 75 MHz 13C
NMR (CDCI3) 5 206.38, 132.46, 122.93, 64.53, 63.25, 40.54,
38.16, 32.17, 25.65 ,25.28, 23.67, 22.30, 16.05, 13.74; IR
(neat) 2961, 2931, 2873, 1722, 1454, 1407, 1382, 1249, 1133,
1068 cm-1; MS (Cl), m/e (relative intensity) 224 (m+, 1.8),
223(20), 205(2), 157(2), 143(6), 141(5), 139(8), 137(3),
125(8), 121(7); HR MS (Cl) 223.1657 (calc, for Ci4H2302:
223.1698).
General Procedure for Cvclizations of Epoxy Ketones
The appropriate a,P~epoxy ketone (1.0 mmol) was weighed
into a 10 ml pear-shaped flask (PSF) Then TBTH (2.0 mmol),
AIBN (0.1 mmol), and benzene (2.0 ml) were added to the same


90
flask. This mixture was degassed for 20 min. After it was
degassed, the temperature was raised to 85C. After the
starting material had been consumed, the reaction was
concentrated and purified by column chromatography to yield
the cyclized products.
(2-Hydroxy-5-isopropyl-2-methylcyclopentyl)ethanone
This compound was isolated as a mixture of two products
in a 3:2 ratio (1H NMR integration) The isomers were not
fully separated by column chromatography. The combined yield
for both compounds was 82.7%. Despite the chromatography
problems some fractions did contain pure compound and the
spectra for each are reported below.
Major Product (189): Rf 0.31 (50% Et20/hexane); 300 MHz
!h NMR
(CDCI3)
8 2.88 (1H,
s), 2.65
(1H, d, J=
=10
Hz), 2.38
(1H, m)
, 2.27
(3H, s), 1.94
(1H, m) ,
1.83-1.48
(4H,
m), 1.34
(3H, s)
, 0.84
(6H, dd, J=7,
12 Hz);
75 MHz 13C
NMR
(CDCI3) 5
213.67, 81.22, 64.61, 49.60, 41.45, 33.02, 32.07, 21.IQ,
26.08, 21.51, 19.38; IR (neat) 3446, 2959, 2872, 1699, 1466,
1422, 1369, 1245, 1170, 1129 cm-1; MS (Cl), m/e (relative
intensity) 185(m++l,100), 184(1), 168(5), 167(50), 149(3),
141(2), 123(9), 109(1); HR MS (Cl) 185.1526 (calc. for
C11H21O2 : 185.1541) .
Minor Product (190) : Rf 0.25 (50% Et2/hexane); 300 MHz
!h NMR
(CDCI3)
5 2
.80 (1H, d,
J=9 Hz),
2.26 (3H, s), 2.24
(1H
m) 1 .
75 (4H,
m) ,
1.50 (2H,
m), 1.18
(3H, s), 0.84 (6H,
dd
J=7.5,
17 Hz);
75
MHz 13C NMR
(CDCI3)
8 210.72, 81.59, 66
.76


91
47.00, 42.49, 32.SI, 32.26, 26.03, 24.61, 21.29, 20.10; IR
(neat) 3462, 2960, 2872, 1702, 1466, 1368, 1242, 1167, 1127,
932 cm-1; MS (Cl), m/e (relative intensity) 185(m+ +1,61) ,
169(2), 168(11), 167(100), 165(1), 149(8), 141(2), 124(1),
123 (16), 109 (3); HR MS (Cl) 185.1545 (calc, for CnH2i02:
185.1541) .
1-(2-Hydroxy-5-isopropyl-2-methylcyclopentyl)-1-pentanone
This compound was isolated as a mixture of two products
in a 1:1 ratio (by isolated weights). The combined yield for
both compounds was 81.5%. The spectra for each are reported
below.
Major Product (191) : Rf 0.48 (50% Et20/hexane); 300 MHz
l-H NMR (CDCI3) 5
3.10
(1H,
s) ,
2.63 (1H,
d, J=ll
Hz), 2.54
(2H, t, J=7 Hz),
2.49
(1H,
m) ,
2.00-1.50
(7H, m) ,
1.35 (2H,
m) 1.31 (3H, s), 0.92 (3H, t, J=7 Hz), 0.85 (6H, dd, J=7, 13
Hz); 75 MHz 13C NMR (CDC13) 5 215.94, 81.26, 63.83, 49.81,
45.86, 41.46, 31.74, 27.78, 25.80, 25.23, 22.28, 21.60,
19.14, 13.86; IR (neat) 3481, 2959, 2872, 1692, 1466, 1370,
1129, 1073, 942 cm-1; MS (Cl), m/e (relative intensity)
227(m++l,100), 219(6), 210(9), 209(65), 191(8), 183(4),
149(7), 127(11), 124(4), 123(55); HR MS (Cl) 227.2015 (calc,
for Ci4H2702: 227.2011).
Minor Product (192): Rf 0.40 (50% Et20/hexane); 300 MHz
XH NMR (CDCI3) 5 2.78 (1H, d, J=9 Hz), 2.60-2.41 (2H, m), 2.23
(1H, m), 1.92-1.42 (8H, m) 1.32 (2H, m), 1.15 (3H, m) 0.93
(3H, t, J=8 Hz), 0.83 (6H, dd, J=7, 18 Hz); 75 MHz 13C NMR


92
(CDC13) 5 212.62, 81.75, 66.07, 47.18, 44.83, 42.50, 32.82,
26.01, 25.41, 24.80, 22.30, 21.33, 20.02, 13.89; IR (neat)
3474, 2958, 2872, 1694, 1466, 1377, 1307, 1244, 1109, 1068
cm-1; MS (Cl), m/e (relative intensity) 227 (m++l, 11) 226(2),
214(1), 211(1), 210(6), 209(53), 208(1); HR MS (Cl) 227.1999
(calc, for C14H27O2: 227.2011).
2-Hydroxy-5-isopropy1-2-methylcyclopentanecarboxaldehyde
This compound was isolated as a mixture of two products
in a 3:1 ratio (1H NMR integration and Capillary GC) The
isomers were not fully separated by column chromatography,
and the combined yield for both compounds was 81%. Despite
the chromatography problems some fractions did contain pure
compound and the spectra for each are reported below.
Major Product (198): Rf 0.31 (50% Et20/hexane); 300 MHz
iH NMR (CDCI3) 5 9.80 (1H, s) 2.46 (1H, m), 2.30 (1H, d, J=9
Hz), 2.13 (2H, m) 1.8-1.4 (4H, m) 1.42 (3H, s), 0.88 (6H,
dd, J=7, 13 Hz); 75 MHz 13C NMR (CDC13) 5 206.01, 82.78,
64.42, 46.78, 41.67, 32.26, 27.85, 26.83, 21.18, 19.99; IR
(neat) 3437, 2960, 2872, 2730, 1715, 1466, 1378, 1268, 1136,
1074 cm-1; MS (Cl), m/e (relative intensity) 171(m++l,7),
169(4), 155(8), 154(5), 153(69), 137(12), 135(23), 127(12),
114(4), 100(11); HR MS (Cl) 173.1354 (calc, for C10H19O2:
171.1385) .
Minor Product (199): Rf 0.25 (50% Et20/hexane); 300 MHz
!h NMR (CDCI3) 5 9.70 (1H, d, J=3 Hz), 2.54 (1H, dd, J=3, 7
Hz), 2.18 (1H, m) 1.9-1.5 (5H, m) 1.32 (3H, s), 1.25 (1H,


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