(E)- And (Z)-1-(Phenylsulfonyl)-4-(trimethylsilyl)-2-butenes: Synthetic Equivalents for the 1-(1,3-Butadienyl) Anion and the 1,1-(1,3-Butadienyl) Dianion

Article abstract of DOI:10.1021/jo970545k

(E)- and (Z)-1-(phenylsulfonyl)-4-(trimethylsilyl)-2-butenes (7 and 8) are converted by n-BuLi to (E)- and (Z)-1-lithio-1-(phenylsulfonyl)-4-(trimethylsilyl)-2-butenes (15 and 16) with retention of initial stereochemistries. Reactions of 15 and 16 with electrophiles (protio and deuterio acids, primary, secondary, and benzyl halides, chloroformates, chlorothioformates, acid chlorides, epoxides, trialkylsilyl chlorides, and triethylgermanyl chloride) in THF or THF/HMPA give the corresponding (E)- and (Z)-1-(phenylsulfonyl)-1-substituted-4-(trimethylsilyl)-2-butenes (32) with stereochemical retention. That β,γ-unsaturated silyl sulfones 32 are formed instead of their α,β-unsaturated (conjugated) isomers are attributed to stabilizing multiple anionic and cationic hyperconjugation and to steric effects as in 29-31. Of importance in synthesis is that 32 are eliminated by TBAF at -20 to 0°C, thermally, or by column chromatography to (E)- (100 to > 93%) rather than (Z)-1-substituted-1,3-butadienes (38). Further, 32 undergo conversions by n-BuLi and various alkylating agents to (unconjugated) 1-(phenylsulfonyl)-1,1-disubstituted-4-(trimethylsilyl)-2-butenes (46) with retention of stereochemistry. Eliminations of 46 by fluoride ion, acid catalysis, or heat yield 1,1-disubstituted-1,3-butadienes (53). Silyl sulfones 7 and 8 are thus synthetic equivalents for the (E)-1-(1,3-butadienyl) anion (44) and the 1,1-(1,3-butadienyl) dianion (57). Silyl sulfones 7 and 8 also undergo efficient stereospecific intramolecular conversions by n-BuLi and α,ω-dihalides to 1,1-cycloalka-1-(phenylsulfonyl)-4-(trimethysilyl)-2-butenes (62 and 71) that are eliminated by fluoride ion, heat, or adsorption chromatography to 1,1-cycloalka-1,3-butadienes (72).

Full text of DOI:10.1021/jo970545k

J . Org. Chem. 1998, 63, 4181-4192
4181
(E)- a n d (Z)-1-(P h en ylsu lfon yl)-4-(tr im eth ylsilyl)-2-bu ten es:
Syn th etic Equ iva len ts for th e 1-(1,3-Bu ta d ien yl) An ion a n d th e
1,1-(1,3-Bu ta d ien yl) Dia n ion
Timothy P. Meagher, Larry Yet, Chi-Nung Hsiao, and Harold Shechter*
Department of Chemistry, The Ohio State University, Columbus, Ohio 43210
Received March 25, 1997
(E)- and (Z)-1-(phenylsulfonyl)-4-(trimethylsilyl)-2-butenes (7 and 8) are converted by n-BuLi to
(E)- and (Z)-1-lithio-1-(phenylsulfonyl)-4-(trimethylsilyl)-2-butenes (15 and 16) with retention of
initial stereochemistries. Reactions of 15 and 16 with electrophiles (protio and deuterio acids,
primary, secondary, and benzyl halides, chloroformates, chlorothioformates, acid chlorides, epoxides,
trialkylsilyl chlorides, and triethylgermanyl chloride) in THF or THF/HMPA give the corresponding
(E)- and (Z)-1-(phenylsulfonyl)-1-substituted-4-(trimethylsilyl)-2-butenes (32) with stereochemical
retention. That â,γ-unsaturated silyl sulfones 32 are formed instead of their R,â-unsaturated
(conjugated) isomers are attributed to stabilizing multiple anionic and cationic hyperconjugation
and to steric effects as in 29-31. Of importance in synthesis is that 32 are eliminated by TBAF
at -20 to 0 °C, thermally, or by column chromatography to (E)- (100 to > 93%) rather than (Z)-
1-substituted-1,3-butadienes (38). Further, 32 undergo conversions by n-BuLi and various
alkylating agents to (unconjugated) 1-(phenylsulfonyl)-1,1-disubstituted-4-(trimethylsilyl)-2-butenes
(46) with retention of stereochemistry. Eliminations of 46 by fluoride ion, acid catalysis, or heat
yield 1,1-disubstituted-1,3-butadienes (53). Silyl sulfones 7 and 8 are thus synthetic equivalents
for the (E)-1-(1,3-butadienyl) anion (44) and the 1,1-(1,3-butadienyl) dianion (57). Silyl sulfones 7
and 8 also undergo efficient stereospecific intramolecular conversions by n-BuLi and R,ω-dihalides
to 1,1-cycloalka-1-(phenylsulfonyl)-4-(trimethysilyl)-2-butenes (62 and 71) that are eliminated by
fluoride ion, heat, or adsorption chromatography to 1,1-cycloalka-1,3-butadienes (72).
In tr od u ction
(Z)-1-(phenylsulfonyl)-4-(trimethylsilyl)-2-butenes (7 and
8) to give 1-substituted and 1,1-disubstituted 1,3-buta-
dienes 9 and 10 are now described.2 The objective of this
program is to develop advantageous methodology for
preparing functionally substituted conjugated dienes.
Vicinal silylsulfonylethanes 3 and 5 (eqs 1 and 2),
readily prepared from 1-(phenylsulfonyl)-2-(trimethylsi-
lyl)ethane (1), n-BuLi, and electrophiles, are of value
because fluoride ion effects their eliminations to 1-sub-
stituted and 1,1-disubstituted ethenes 4 and 6, respec-
tively, at 0-65 °C.1 In further development of advanta-
Resu lts a n d Discu ssion
Silylsulfonylbutenes 7 and 8 (eq 3) are prepared in 41-
62% yields by (1) addition of [(trimethylsilyl)methyl]-
magnesium chloride (11) to acrolein and acidification to
give 4-(trimethylsilyl)-1-buten-3-ol (12, 68%),3a (2) depro-
tonation of 12 by n-BuLi and displacement of phenyl-
sulfenyl chloride at -78 °C to produce (E)- and (Z)-
(silylsulfinyl)-2-butenes 14 (70-85%)3b via 2,3-sigmatropic
rearrangements of phenylsulfenate intermediate 13, and
(3) oxidation of sulfoxides 14 (77-85%) with MCPBA in
geous desulfonylsilylation methodology, syntheses and
various substitution and elimination reactions of (E)- and
(2) (a) The initial results of the present study were communicated
by the following: Hsiao, C.-N.; Shechter, H. Tetrahedron Lett. 1984,
25, 1219. (b) The possible utility of tetrabutylammonium triphenyldi-
fluorosilicate [Bu4N(C6H5)3SiF2] for elimination of 3, 5, 32, and 6 has
as yet not been determined.2c,d (c) Pilcher, A. S.; Ammon, H. J .;
DeShong, P. J . J . Am. Chem. Soc. 1995, 117, 5166. (d) Pelcher, A. S.;
DeShong, P. J . Org. Chem. 1996, 61, 6901.
(1) (a) Kocienski, P. J . Tetrahedron Lett. 1979, 2649. (b) Kocienski,
P. J . J . Org. Chem. 1980, 45, 2037. (c) Hsiao, C.-N.; Shechter, H.
Tetrahedron. Lett. 1982, 3455. (d) Eisch, J . J .; Behrooz, M.; Dua, S. K.
J . Organomet. Chem. 1985, 285, 121. (E) Hsaio, C.-N.; Shechter, H. J .
Org. Chem. 1988, 53, 2688. (f) Kim, S. H.; J in, Z.; Ma, S.; Fuchs, P. L.
Tetrahedron Lett. 1995, 4013 and references therein.
S0022-3263(97)00545-8 CCC: $15.00 © 1998 American Chemical Society
Published on Web 06/05/1998

4182 J . Org. Chem., Vol. 63, No. 13, 1998
Meagher et al.
methylene chloride at 0 °C. The E:Z ratios of 7 and 8
usually range from 77:23 to 88:12. If needed, chroma-
tography allows separation of pure 7 from mixtures of 7
and 8.
Incorporation of a single deuterium atom into the
R-positions of 7 and 8 was determined to be ∼87% by
comparing the area of the deuterium-coupled 1H NMR
doublet in the δ 3.75 region with that for trimethylsilyl
(δ ) 0.00). High-resolution mass spectral analyses of 19
and 20 resulting from loss of phenylsulfinate ions in 17
and 18 reveal that the cations are formed in a ratio of
84:16 which agrees closely with the 87:13 deuterium
value obtained from the 1H NMR peak area integrations.
(E)- and (Z)-silyl sulfones 7 and 8 were then dideuter-
ated with D2O as follows. First, 7 and 8 were deproto-
nated with n-BuLi in THF at -78 °C. The solution was
warmed slowly to room temperature, quenched with
excess D2O, and then worked up after 12.5 h. The only
products detected are 1,1-dideuterio-2-butenes 21 and 22
in 89% yield. Dideuteration of the R-positions in 7 and
n-BuLi (1 equiv) in THF converts 7 and 8 at -78 °C to
lithio derivatives 15 and 16 which, when warmed to 20-
25 °C for ∼30 min and quenched with D2O (1 equiv), give
deuterio derivatives 17 and 18 in 85% yield. If 15 and
16 in THF are kept at 25 °C for 3.3 h before deuteration,
considerable decomposition occurs and the yields of
deuterio products 17 and 18 are reduced to 47%. Lithio
derivatives 15 and 16 are stable for only short periods
at higher temperatures.
8 is apparent from inspection of the δ 3.7 regions of the
1H NMR spectra of 21 and 22 which show only small
(<5%) residual H absorptions. Dideuteration obviously
arises after deprotonation of 17 and 18 by the lithium
deuteroxide generated in quenching of 15 and 16. Fur-
ther illustration of rapid protium-deuterium exchange
in which carbon-carbon double bonds do not move into
conjugation with phenylsulfonyl groups is that dideute-
riosilyl sulfones 21 and 22 are converted by H2O/LiOH/
THF to silyl sulfones 7 and 8 of natural deuterium
abundances within 16 h.
The facts that the unconjugated silylsulfonyl-2-butenes
7 and 8 do not rearrange significantly to their conjugated
sulfone isomers, (E)- and (Z)-1-butenes 23 and 24, or
undergo deuterium incorporation to form (E)- and (Z)-3-
deuterio-1-butenes 25 and (E)- and (Z)-3,3-dideuterio-1-
butenes 26 raise significant points. â,γ-Unsaturated
The structures, stereochemistries, and deuterium con-
tents of 17 and 18 were determined by spectral methods.
The proton-decoupled 13C NMR of 17 and 18 has distinct
sets of absorptions for each isomer. The ratios of the
peak heights for comparable carbon atoms in the mix-
tures of 17 and 18 obtained from 7 (77%) and 8 (23%)
1
range from 77:23 to 83:17. The H NMR of 17 and 18 at
250 MHz reveals absorptions at δ 5.56 and 5.76, respec-
tively, and couplings between Hb and Ha of 15.2 and 10.7
Hz, respectively. The E:Z ratio of 17 and 18 found by
1H NMR is 79:21 and agrees with that determined by
13C NMR. There is no significant change in the positions
of and the stereochemistries about the carbon-carbon
double bonds upon conversions of 7 and 8 to deuterio
derivatives 17 and 18.
(3) (a) Prepared initially by Sommer, L. H.; Goldberg, G. M.;
Whitmore, F. C. J . Am. Chem. Soc. 1946, 68, 481. (b) The concentration
of chloromethyltrimethylsilane in Et2O or THF greatly affects the yield
of 9 upon reaction with magnesium. When the (chloromethyl)trimeth-
ylsilane is ∼3.33 M, the yield of 9 is ∼95%. Under very dilute
conditions, the yield of 9 is greatly lowered. (b) Phenylsulfenyl chloride
should be added slowly so as to maintain the reaction temperature
below -60 °C. At higher temperatures side products are formed which
reduce the yield and make purification of 12 difficult.
(nonconjugated) sulfones 27 are more stable than their
R,â-unsaturated (conjugated) isomers 28.4 Hine et al.
have suggested that 28 are not highly stabilized because
sulfonyl groups are weak conjugaters.4 Now emphasized,

(E)- and (Z)-1-(Phenylsulfonyl)-4-(trimethylsilyl)-2-butenes
J . Org. Chem., Vol. 63, No. 13, 1998 4183
Ta ble 1. Rea ction s of 1-Lith io Der iva tives 15 a n d 16 of
(E)- a n d (Z)-1-(P h en ylsu lfon yl)-4-(tr im eth ylsilyl)-
2-bu ten es (7 a n d 8) w ith Electr op h iles (eq 4)
Ta ble 2. F lu or id e Ion Elim in a tion s (eq 5) of (E)- a n d
(Z)-1-(P h en ylsu lfon yl)-1-su bstitu ted -4-(tr im eth ylsilyl)-
2-a lk en es (32-35)
a
The E/Z ratios were determined from 1H NMR as described
in the text. Yields of isolated products. c The E/Z ratios were
b
determined by high-field 1H and 13C NMR methods. The stere-
d
a
The E/Z ratios were calculated from 1H NMR as described in
ochemistries of 32j-m , 33, and 34 are unknown.
the text. Yields of isolated products. c Reactions were conducted
in THF/HMPA. The stereochemistries of the products are un-
b
d
in THF to yield (E)- and (Z)-2-nonenes 32c. HMPA
accelerates alkylation of 1-bromopentane at -78 °C.
Increases in the reaction temperatures (-20 to 23 °C)
result however in significant decomposition of 15 and 16
and lower yields of alkylation products 32c. Reactions
of 15 and 16 with 1-bromo-2-methylpropane (Table 2,
entry 4), a slightly hindered halide, occur satisfactorily
in THF/HMPA at -78 °C to produce (E)- and (Z)-2-
heptenes 32d . Synthesis of 1-substituted 2-butenes 32
(E1 ) alkyl) from sodio analogues of 15 and 16 prepared
from reactions of 7 and 8 with sodium hydride or sodium
amide in THF is unsatisfactory. The insolubilities of
these bases in THF limit deprotonations of 7 and 8 to
temperatures of 0 °C and above, and under such condi-
tions, thermal decompositions of sodio analogues of 15
and 16 become excessive.
known.
in addition to steric effects, are that important factors
in the greater thermodynamic stabilities of 7 and 8 over
23 and 24 are multiple anionic and cationic hyperconju-
gation as illustrated in part in 29-31.5 Similar signifi-
cant hyperconjugative effects may be operational in 17,
18, 21, 22, and 27 and in other â,γ-unsaturated systems.5
Alkylations of 15 and 16 by 2-bromopropane, a second-
ary halide (Table 1, entry 5), in THF/HMPA yield (E)-
and (Z)-2-hexenes 32e (97%). The more hindered sec-
ondary bromide, 2-bromo-1-phenylpropane, behaves as
expected in that diastereomeric substitution products (E)-
and (Z)-2-hexenes 33 and 34 (40%) are formed along with
Study was then made of reactions of lithio derivatives
15 and 16 with electrophiles to give (E)- and (Z)-1-
substituted-2-butenes 32 (eq 4). Methyl iodide and
benzyl bromide (Table 1, entries 1 and 2) alkylate 15 and
16 efficiently at C-1 at -78 °C in THF to give (E)- and
(Z)-2-pentenes 32a and (E)- and (Z)-5-phenyl-2-pentenes
32b, respectively. The yellow colors of solutions of lithio
(E)-1-phenyl-1-propene (26%) and 7 and 8 (33%). Fur-
ther, bromocyclohexane and cyclohexyl tosylate are dis-
placed by 15 and 16 to give (E)- and (Z)-1-cyclohexyl-2-
butenes 35 slowly and inefficiently (35-27%). During
reactions of bromocyclohexane with 15 and 16, 35 is
converted in part to (E)-1-cyclohexyl-1,3-butadiene (36,
reagents 15 and 16 are discharged within 1 min after
addition of the alkyl halides, and the yields of 32a and
32b are excellent. 1-Bromopentane (Table 1, entry 3)
reacts much slower than the previous halides at -78 °C
(5) (a) Only a portion of the cationic hyperconjugative forms involv-
ing Me3Si+ and H+ and anionic hyperconjugative forms involving
-O2S-Ph has been illustrated. This concept will be developed further
in publications from this laboratory. (b) Baker, J . W. Hyperconjugation;
Oxford University Press: London E.C., 1952; Vol. 4, p 58. (c) Shechter,
H.; Shepherd, J . W. J . Am. Chem. Soc. 1954, 76, 2716.
(4) (a) Hine, J .; Linden, S.-M.; Wang, A.; Thiagarajan, V. J . Org.
Chem. 1980, 45, 2821. (b) Hine, J .; Skoglund, M. J . J . Org. Chem. 1982,
47, 4766. The equilibrium constant, K1, for trans-n-butyl 2-butenyl
sulfone/trans-n-butyl 1-butenyl sulfone in t-BuOH at 25 °C is 40 ( 15;
-∆G ) 2.2 ( 0.3 kcal/mol.

4184 J . Org. Chem., Vol. 63, No. 13, 1998
Meagher et al.
13%), 7 and 8 (7-30%), and cyclohexene and much of the
bromocyclohexane is recovered. Attempts to improve
coupling of secondary halides with 15 and 16 by addition
of cupric chloride or cuprous iodide give complex product
mixtures.
give cyclohexanols 32j in 83% yield after neutralization.
Three pairs of diastereomers in a ratio of 12:46:42 are
1
indicated for 32j by the H NMR Ha sulfone absorbances
at δ 4.55, 4.15, and 3.55 downfield from that of tetra-
methylsilane. High-field 13C NMR reveals however that
32j consists of four pairs of diastereomers, one pair in
small amounts. Column chromatography results in
isolation of the most polar diastereomeric pair from 32j
as a white crystalline solid. The structures of the
diastereomers of 32j cannot be designated further as yet.
Propylene oxide (Table 1, entry 11), an unsymmetrical
epoxide, undergoes regiospecific alkylation at its meth-
ylene group upon reaction with 15 and 16 at 23 °C in
THF to give, after acidification, 5-hepten-2-ols 32k (59%).
Similarly, 15 and 16 effect sterically directed ring open-
ings of 1,2-epoxybutane (Table 1, entry 12) and styrene
oxide (Table 1, entry 13) to yield 6-octen-3-ols 32l (52%)
and 4-hexen-1-ols 32m (54%), respectively, upon neu-
tralization. The stereochemistries of 32k , 32l, and 32m
The E:Z ratios of 32a , 32c, and 32d (eq 4, Table 1)
have been determined by high-field 1H NMR methods.
The Hb absorptions of the Z-isomers of the above product
pairs are doublets of triplets at δ 5.0-5.2 and couple to
Ha by ∼9 Hz. For the corresponding E-isomers, the
resonances of Hb are doublets at δ 5.55 which are coupled
by ∼13 Hz to Ha. The stereochemistries of 32b, 32e, and
35 cannot be designated directly because their olefinic
1H NMR absorptions are not adequately resolved. The
structures are assignable however by 13C NMR on the
premise that the E-isomer of a product pair obtained from
7 and 8 is always major. Of further importance in
alkylations and cycloalkylations of 15 and 16 (Table 1)
is that the stereochemistries of the products are es-
sentially identical with those of initial 7 and 8. Such
retentions in the geometries of highly conjugated allylic
anionic systems have been previously observed in base-
catalyzed R-alkylations of (E)- and (Z)-3-alkenoate esters6
and of (E)-1-phenylsulfonyl-2-pentene.6
Reactions of acid chlorides with lithio derivatives 15
and 16 are satisfactory. Additions of ethyl chloroformate,
ethyl chlorothioformate, and trimethylacetyl chloride
(Table 1, entries 6-8) to 15 and 16 in THF at -78 °C
result in rapid displacements to give 1-carbalkoxy-,
1-carbothioalkoxy-, and 1-acyl-2-butenes 32f, 32g, and
32h , respectively, in 45-75% yields. Each product pair
exhibits two sets of 13C NMR (63 MHz) absorptions, one
set for each geometrical isomer. The E:Z ratio of 32f
(Table 1) is determined after integration of the (CH3)3Si
1H NMR singlets at δ 0.06 (Z) and -0.01 (E) or the
R-silylmethylene hydrogen doublets at δ 1.48 (J ) 7.0
Hz, Z) and 1.55 (J ) 7.4 Hz, E). Similarly, the E:Z ratio
of 32g (Table 1) is obtained upon integration of the
doublets at δ 4.56 (J ) 8.5 Hz, E) and 4.80 (J ) 8.5 Hz,
Z). Of value is that 32h separates cleanly on column
chromatography to give its (E)- and (Z)-isomers in 59 and
16% yields, respectively. Further, the E:Z ratios (Table
1) of 32g-h are similar to those of the 7 and 8 used in
the preparations and thus there are no significant
stereochemical changes in the above transformations of
lithio derivatives 15 and 16 (eq 4). The silylsulfonyl-3-
penten-1-one 32i (Table 1, entry 9) obtained from 15 and
16 (80:20) and benzoyl chloride is a single isomer however
and is presumed to be of E-stereochemistry. The reason
32i is the exclusive product of benzoylation of 15 and 16
has not been established.7
1
could not be established by H and 13C NMR methods.
The products were used directly in elimination experi-
ments as will be described later.
Reactions of lithio derivatives 15 and 16 with trialkyl-
germanyl and trialkylsilyl chlorides have been studied.
Triethylgermanyl chloride (Table 1, entry 14) reacts at
23 °C in THF/HMPA with 15 and 16 to give (E)- and (Z)-
1-(triethylgermanyl)-2-butenes 32n (35%). Similarly,
trimethylsilyl chloride (Table 1, entry 15) is displaced by
15 and 16 at 23 °C in THF to yield (E)- and (Z)-1,4-bis-
(trimethylsilyl)-2-butenes 32o (51%). Although the reac-
tion yields have not been maximized, the E:Z ratios of
32n and 32o as found from 1H NMR and 13C NMR
correspond (Table 1) to that of the 7 and 8 used in the
syntheses. Tri(2-propyl)silyl chloride (Table 1, entry 16),
a sterically hindered reactant, is essentially inert to 15
and 16 in a 77:21 ratio in THF at 23 °C for 4 h. Addition
of HMPA (5 molar equiv) however results in greatly
accelerated silylations of 15 and 16 to give 1-(tri(2-
1
propyl)silyl)-2-butene 32p (33%) which H and 13C NMR
reveal to be a single and presumably the E-isomer.
Exclusive formation of (E)-32p presumably arises be-
cause reaction of tri(2-propyl)silyl chloride occurs much
more rapidly with 15 than with 16.
Eliminations of (E)- and (Z)-1-substituted 2-butenes 32
(eq 5) to 1-substituted 1,3-butadienes 38 have been
studied. Additions of commercial TBAF (1.5-2.0 molar
equiv) to 32 (Table 2) in THF or Et2O at 0 °C result in
near-instantaneous formations of conjugated dienes 38
(eq 5) in 52-75% yield along with trimethylsilyl fluoride
(39) and phenylsulfinate ion (40). At -20 °C reaction
Reactions of lithio reagents 15 and 16 with epoxides
were then developed. Cyclohexene oxide (Table 1, entry
10) is ring-opened by 15 and 16 in Et2O at -78 °C to
times increase to ∼1 h. If less than 1.5 equiv of TBAF is
used, initial 32 remains. The elimination method (eq 5,
Table 2) usually works well with commercial TBAF which
contains much water and with silyl sulfones that contain
(6) Cunico, R. F.; Han, Y.-K. J . Organomet. Chem. 1976, 105, C29.
(7) Among the many possibilities are that (E)-32i had been produced
in better yield and/or undergoes elimination faster than (Z)-32i.

(E)- and (Z)-1-(Phenylsulfonyl)-4-(trimethylsilyl)-2-butenes
J . Org. Chem., Vol. 63, No. 13, 1998 4185
alkyl, arylalkyl, cycloalkyl, ester, ketone, or hydroxyl
groups (see Experimental Section). For 32 which elimi-
nate to highly volatile, conjugated dienes that cannot be
separated easily from THF or Et2O, the reactions can be
accomplished efficiently in DMSO at 23 °C. Thus, 32a
and 32e are converted by TBAF (Table 2) in DMSO and
flash distillations to (E)-1,3-pentadiene (38a , 76%) and
(E)-5-methyl-1,3-hexadiene (38e, 85%), respectively.
The behavior of fluoride ion with (E)- and (Z)-1,4-bis-
(trimethylsilyl)-2-butenes (32o) is different than that
with 32a -m , 33, 34, and 35 (Table 2). Reaction of 32o
with TBAF (2 equiv) at 0 °C gives (E)-1-(phenylsulfonyl)-
4-(trimethylsilyl)-2-butene (7, eq 6, 70%) by attack of
fluoride ion on the trimethylsilyl groups at the 1-positions
and then aqueous workup. (E)-1-(Trimethylsilyl)-1,3-
butadiene (43, eq 7), the conjugative elimination product,
is not produced. (E)-1-(Phenylsulfonyl)-4-(trimethylsilyl)-
(eq 5) other than that the reactions are rapid. Although
conjugative 1,4-elimination reactions usually occur more
rapidly by cis than trans processes,8 cis- and/or trans-
desulfonylsilylations of 32 with steric control by the
substituent at C-1 can give products (E)-38 essentially
exclusively. Further studies of the stereochemistries of
eliminations of (silylsulfonyl)alkenes are in progress.
Investigation has also been made of other fluorides and
other reagents which effect conjugative eliminations of
32. Potassium fluoride does not eliminate 32b (Table 2)
or 35 in refluxing acetonitrile (bp 81.6 °C) in 24 h. The
lack of reaction in these experiments is due to the
insolubility of the fluoride reagent. Potassium fluoride
and 32b (Table 2) in refluxing acetonitrile for 16 h in
the presence of the phase-transfer reagent, cetyltri-
methylammonium bromide, give 38b however in 63%
yield. Similarly, addition of tris[2-(2-methoxyethoxy)-
ethyl]amine (TDA-1, an acyclic cryptand) to 35 and
potassium fluoride in refluxing acetonitrile yields 36
(Table 2, 65%).9 The (E) and (Z) ratios of the 38b and
1
the 36 produced, as determined from their olefinic H
NMR coupling constants, are >99:1, respectively. Potas-
sium fluoride in combination with phase-transfer re-
agents therefore is a satisfactory alternate to TBAF for
eliminations of 32 if the higher reaction temperatures
and the longer reaction times are unimportant. Alumi-
num chloride, when used in molar excess quantities (3
equiv) in methylene chloride at -78 °C, eliminates 32b
to 38b (Table 2; E:Z ratio of >9:1) in 29% yield. The
aluminum chloride methodology suffers in that the 38b
formed reacts extensively with the Lewis acid present.10
Further, the eliminative behavior of 32b in the presence
of boron trifluoride is unsatisfactory.
1-[tri(2-propyl)silyl]-2-butene (32p ) however has its sili-
con at C-1 highly encumbered and is not attacked by
fluoride ion as is 32o (eq 6). Satisfactory 1,4-elimination
of 32p thus does occur with TBAF (2 equiv) at 20-23 °C
in <15 min to yield the single geometric isomer, (E)-1-
[(tri-2-propyl)silyl]-1,3-butadiene (38p , eq 5, Table 2,
61%). Generally, conjugative desulfonylsilylation of 32
(Table 2) is an excellent low-temperature method for
preparing 1-substituted-1,3-butadiene derivatives 38 (eq
5), and thus 7 and 8 are effective synthetic equivalents
for the 1-(1,3-butadienyl) anion (44).
Attention next turned to practical alkylative conver-
sions of various 1-substituted-2-butenes 32 to 1,1-disub-
stituted derivatives 46 (eq 8). 2-Butenes 7 and 8 are
found to be converted in a one-pot procedure to (E)- and
(Z)-2-pentenes 47 in 98% yield from (1) lithio intermedi-
ates 15 and 16 in THF with methyl iodide (1 equiv) at
-30 °C, (2) addition of n-BuLi (1 equiv) at -78 °C, and
(3) reaction with methyl iodide (1.5 equiv) at 20-25 °C.
The stereochemistries of (E,Z)-47 could not be assigned
by 1H NMR because the absorptions of their olefinic
protons (δ 5.2-5.7) overlap.
1
High-field H and 13C NMR methods reveal that almost
all of the elimination products (Table 2) are totally (100%)
or near totally (98 to >99%) single geometric isomers.
13C NMR evidence does indicate that 38d and 38q
contain second isomers (Table 2) in 7% and 4% amounts.
1
Of note are that the H NMR absorptions (250 MHz) of
the olefinic hydrogens in 38a -q and 36 (Table 2) are
cleanly separated and the single or the major dienes are
assigned E-stereochemistries on the basis of coupling
constants (J cd) of 14.8-16.3 Hz for protons Hc and Hd as
represented in 38 in eq 5. Elimination of silyl sulfones
32 by fluoride ion is therefore clearly an excellent method
for preparing (E)-1-substituted-1,3-dienes (38), and thus
7 and 8 can be described more completely as practical
synthetic equivalents for the (E)-1-(1,3-butadienyl) anion
(44). What is not yet clear, however, are the detailed
mechanisms of conversions of 32 by fluoride ion to 38
Alkylation was then extended to 32b (E1 ) CH2C6H5,
Table 1). Deprotonation of 32b (E:Z ) 79:21) with
n-BuLi, reaction with methyl iodide, workup, and chro-
(8) Hill, R. K.; Bock, M. G. J . Am. Chem. Soc. 1978, 100, 637.
(9) (a) Soula, G. J . Org. Chem. 1985, 50, 3717. (b) TDA-1 was
obtained from the Aldrich Chemical Co., Milwaukee, WI.
(10) Reaction was effected by adding AlCl3 (769 mg, 5.76 mmol) to
32b (806 mg, 2.25 mmol) in CH2Cl2 (10 mL) at -78 °C, stirring (0.5
h), and then adding pentane (20 mL) and water.

4186 J . Org. Chem., Vol. 63, No. 13, 1998
Meagher et al.
matography give (E)- and (Z)-2-pentenes 48 in an 80:20
ratio in 97% yield. The geometric assignments of the
products are based on 1H NMR in that the absorption
for Ha in (E)-48 (δ 5.53, J ab ) 15.6 Hz) is downfield from
that in (Z)-48 (δ 5.41, J ab ) 11.2 Hz). Methylation thus
proceeds with retention of olefinic stereochemistry. Fur-
ther, benzylations of the 1-lithio derivatives of 32b (E1
) CH2C6H5, Table 1) give (E)- and (Z)-dibenzyl deriva-
tives 49 from which (E)-49 can be crystallized in 71%
overall yield from hexane. The stereochemistry of (E)-
R2 ) CH2Ph) result from eliminations of (E,Z)-49 by
either TBAF in THF at 0 °C (83%), aqueous hydrochloric
acid (12 M) at 25 °C, or gas chromatography (>52%).
Further, dienes (E,Z)-51 are obtained from (E,Z)-50 with
TBAF/THF at 0 °C (65%) or by heating. Of note are
reactions of (E,Z)-48 with TBAF in THF at 0 °C to yield
(E)- and (Z)-1,3-pentadienes 56 (75%) for which GC-MS
analysis and NOE reveal that the E:Z ratio is 80:20. The
latter eliminations are emphasized because neither (E)-
48 nor (Z)-48 could be detected immediately after addi-
tion of the TBAF. The rapidities and the efficiencies of
the above elimination reactions at 0 °C are impressive.
Silyl sulfones 7 and 8 therefore are excellent synthetic
equivalents for the 1,1-(1,3-butadienyl) dianion 57 as well
as for 44.
49 is assigned from the olefinic 1H NMR coupling (J ab
17 Hz) between Ha (δ 5.28) and Hb (δ 5.78).
)
1-Bromopentane is of interest because it reacts slowly
with 1-lithio derivatives of 32b (E1 ) CH2C6H5, E:Z )
80:20, Table 1) in HMPA/THF at ∼15 °C to give, after
aqueous workup and column chromatography on silica
gel, the substitution products, (E)- and (Z)-2-nonenes 50,
and elimination products, (E)- and (Z)-1,3-nonadienes 51,
in 61 and 30% yields, respectively.
Synthesis of (E)- and (Z)-1-(3-(trimethylsilyl)-1-prope-
nyl)cyclopropanes 62, possibly as in eq 10, then became
a major objective. Indeed, 15 and 16, when treated with
ethylene oxide (58) at -78 °C followed by methanesulfo-
nyl chloride and refluxing, give mesylates 60. Addition
of n-BuLi then results in lithio derivatives (E,Z)-61 which
ring close to cyclopropanes (E,Z)-62 (28% overall yield
from 15 and 16).
Dialkylates 50 are white solids which display 1H NMR
absorptions for olefinic protons Ha and Hb at δ 5.27 (J ab
) 15.8 Hz) and 5.42 for the E-isomer and at δ 5.12 (J ab
) 12.4 Hz) and 5.67 for the Z-isomer. Disubstitutions
at the C-1 positions in (E,Z)-50 are confirmed since Ha
couple only to Hb. 13C NMR reveals the presence of two
quaternary carbons by absorptions at δ 71.77 (E-isomer)
and 73.37 (Z-isomer). The E:Z ratio of 50 is 79:21 and
therefore essentially identical to that of its 32b precur-
sors.
Dienes 51 are formed simply by conjugative elimina-
tions of (E,Z)-50 during column chromatography.11 1H
NMR, 13C NMR, and GC-MS all indicate that 51 consists
of E- and Z- isomers in a 53-54:47-46 ratio. NOE
experiments reveal cleanly separated absorptions in
(E,Z)-51 at δ 5.88 and 6.05, respectively. Irradiation at
δ 5.88 enhances magnetic resonance of the benzyl protons
at δ 3.39 and thus allows assignment of (E)-51. Irradia-
tion at δ 6.05 amplifies absorption of the allyl protons at
δ 1.99 and therefore the absorbances arise from (Z)-51.
Conjugative eliminations of 1,1-disubstituted-2-butenes
46 to 1,1-disubstituted-1,3-butadienes 53 by fluoride ion
(eq 9), acid catalysis, or heat were then studied as follows.
Tetrahydropyrans (E,Z)-66 are also obtained (8%) from
the above experiment. Formation of 66 presumably
occurs (eq 11) by dilithiation of 15 and 16 by n-BuLi (1.1
equiv), addition of ethylene oxide (58) to 63, reactions of
64 with methanesulfonyl chloride, and then ring closures
of 65 by displacement. Sulfones are known to be dilithi-
ated in their R-positions by n-BuLi.12
(11) (a) The leaving group abilities of sulfones are increased by Lewis
acids. (b) Trost, B. M.; Ghadiri, M. R. J . Am. Chem. Soc. 1984, 106,
7260. (c) Kocienski and Todd [Kocienski, P.; Todd, M. J . Chem. Soc.,
Perkin Trans. 1 1983, 1777] report that certain sulfones eliminate upon
chromatography on silica gel.
Dimethyl(silyl)sulfones (E,Z)-47 are converted to 54 (R1
and R2 ) CH3; 72%) by TBAF in DMSO at 25 °C and
then flash vacuum distillation. Pentadienes 55 (R1 and

(E)- and (Z)-1-(Phenylsulfonyl)-4-(trimethylsilyl)-2-butenes
J . Org. Chem., Vol. 63, No. 13, 1998 4187
chlorobutane, and 1,5-dibromopentane. The monoalky-
lated products formed, 69 [(CH2)nY ) Br(CH2)3, Br(CH2)4,
and Br(CH2)5], are converted by n-BuLi and ring closure
(eq 12) to the corresponding four-, five-, and six-
membered ring (E)- and (Z)-1-(3-(trimethylsilyl)-1-pro-
penyl)cycloalkanes 71 (n ) 3, 4, and 5) in 87, 89, and
78% yields, respectively. Each of the products exhibits
13C NMR absorptions for E- and Z-isomers. The 1H NMR
of the olefinic hydrogens, Ha and Hb, in each product are
well-separated and their chemical shifts (δ 5.29-4.92, J ab
) 15.4-15.9 Hz; δ 5.09-4.70, J ab ) 11.9-11.5 Hz) allow
assignments of the E- and Z-isomers of each pair. The
E:Z ratios for the cyclobutane, cyclopentane, and cyclo-
hexane derivatives 71 (n ) 3, 4, and 5) prepared range
only from 84:16 to 86:14, and thus there is essentially
total retention in the stereochemistries in the above
cycloalkylations of 15 and 16.
Silylsulfonyl eliminations of (E,Z)-62, its four-, five-,
and six-membered ring homologues (E,Z)-71 [(CH2)n, n
) 3, 4, and 5], and tetrahydropyrans (E,Z)-67 were then
investigated. Reactions of (E,Z)-62 with TBAF in DMSO
at 0 °C (eq 13) and flash vacuum distillation yield
Of particular relevance to the present proposal for
formation of 66 is that allyl phenyl sulfone is converted
by n-BuLi (>2 equiv) to 1,1-dilithioallyl phenyl sulfone
(67).12
allylenecyclopropane (72, n ) 2; 90%), a diene of consid-
erable synthetic and theoretical interest.13 Allylene 72
(n ) 2), a polymerizable conjugated diene, is stable for
prolonged periods at -78 °C, and its structure is con-
firmed by comparison with literature properties.13 The
conjugated dienic behavior of 72 (n ) 2) is further
elaborated by effecting its near instantaneous cycload-
dition to 4-phenyl-1,2,4-triazoline-3,5-dione at -78 °C to
give triazolodione 73 (81%).
Cyclopropanes (E,Z)-62 were identified spectroscopi-
cally and from their chemistry as will be described.
Crystallization of the cyclopropanes from hexane gives
a single isomer as evidenced by its single set of 13C NMR
peaks. The 1H NMR of the crystallized product is
complex but integrates for two olefinic protons. Although
the coupling constant, J ab, for the olefinic hydrogens could
not be determined, the pure cyclopropane isolated is
assumed to be (E)-62.
Searches were then made of a better synthesis of cy-
clopropanes (E,Z)-62 and a general method for preparing
their higher cycloalkane homologues. Reactions of 1,2-
dibromoethane [eq 12; 68 ) Br(CH2)2Br] in THF/HMPA
with 15 and 16, as prepared from 7 and 8 of 85:15 ratio,
In extensions of the above methodology, allylenecy-
clobutane (72, n ) 3; 87%) and allylenecyclopentane (72,
n ) 4; 89%) are obtained simply by rapid distillations of
solutions of cyclobutanes (E,Z)-71 (n ) 3) and cyclopen-
tanes (E,Z)-71 (n ) 4) from DMSO containing TBAF.
Further, treatment of cyclohexanes (E,Z)-71 (n ) 5) and
tetrahydropyrans (E,Z)-69 with fluoride ion in THF at 0
°C and chromatography on silica gel result in efficient
production of allylenecyclohexane (72, n ) 5; 78%) and
4-allylenetetrahydropyran (74, 87%), respectively. The
(12) (a) Kaiser, E. M.; Solter, L. E.; Schwarz, R. A.; Beard, R. D.;
Hauser, C. R. J . Am. Chem. Soc. 1971, 93, 4238. (b) Evans, J . B.; Marr,
G. J . J . Chem. Soc., Perkins Trans. 1 1972, 2502. (c) Eisch, J . J .;
Behrooz, M.; Dua, S. K. J . Organomet. Chem. 1985, 285, 121. (d) Gais,
H.-J .; Volhardt, J .; Lukas, K. L. Angew. Chem. 1985, 97, 695 and
references therein. (f) Yet, L. Ph.D. Dissertation, The Ohio State
University, Columbus, OH, 1995. (g) The suggestions of J . J . Eisch
concerning the mechanism of formation of 67 are appreciated.
(13) (a) Blome, H. Dissertation, Bochum, West Germany, 1973. (b)
Brinker, V. H.; Konig, L. J . Am. Chem. Soc. 1979, 101, 4783. (c) Binger,
P.; Germer, A. Chem. Ber. 1981, 114, 3325. (d) Zutterman, F.; Krief,
A. J . Org. Chem. 1983, 48, 1135.
occur smoothly at -78 to 20 °C to give (E)- and (Z)-6-
bromo-2-hexenes 69 [Y(CH2)n ) Br(CH2)2] which are
lithiated by n-BuLi with displacement of lithium bromide
to yield (95%) cyclopropyl derivatives (E,Z)-62 (71; n )
2). Recrystallization of the ring-closure products from
pentane gives the single cyclopropane assigned previously
as (E)-62. The overall synthesis of (E)-62 is excellent.
Reactions of 15 and 16 in an 85:15 ratio with 68 were
extended as in eq 12 to 1,3-dibromopropane, 1-bromo-4-

4188 J . Org. Chem., Vol. 63, No. 13, 1998
Meagher et al.
-78 °C.3b The red color of the phenylsulfenyl chloride disap-
peared immediately on addition. The resulting light yellow
solution was then stirred at room temperature for 2 h, diluted
with Et2O, washed with brine, dried (MgSO4), filtered, and
concentrated in vacuo to a yellow oil (10.9 g). Flash chroma-
tography (silica gel; ethyl acetate:hexanes, 1:2) yielded 12 (7.86
g, 66%), a light yellow liquid: 1H NMR (CDCl3, E- and
Z-isomers) δ -0.03 (s, 9 H), 1.41 (d, J ) 7.8 Hz, 2 H), 1.49 (d,
J ) 8.2 Hz, 2 H), 3.50 (d, J ) 7.5 Hz, 2 H), 5.05-5.15 (m, 1
H), 5.56-5.65 (m, 1 H), 7.47-7.65 (m, 5 H); 13C NMR (CDCl3,
E- and Z-isomers) δ -2.1, -1.9, 19.3, 23.7, 55.5, 60.8, 113.2,
114.4, 124.3, 127.4, 128.9, 130.8, 130.9, 135.1, 137.4, 143.4;
exact mass calcd for C7H15Si (M+ - SOPh) m/e 127.0943, found
m/e 127.0935.
structures of 72 (n ) 3, 4, and 5) and 74 are established
by spectral methods and by comparison with literature
data.13
In conclusion, silyl sulfones 7 and 8 undergo efficient
and stereospecific electrophilic conversions to their cor-
responding 1-substituted (32, eq 4), 1,1-disubstituted (46,
eq 8), and 1,1-cycloalka (71, eq 12) silyl sulfones. Such
substituted silyl sulfones are eliminated by fluoride ion,
thermally, or adsorption chromatography to 1-substituted
(38, eq 5), 1,1-disubstituted (53, eq 9), and 1,1-cycloalka
(72, eq 13) 1,3-dienes, respectively. Silyl sulfones 7 and
8 are therefore of value as synthetic equivalents for 44
and 57. The use of silyl sulfones for preparing o-
quinodimethanes and other unusual dienes advanta-
geously are described in detail in separate publications
from this laboratory.14
(E,7)- a n d (Z,8)-1-(P h en ylsu lfon yl)-4-(tr im eth ylsilyl)-
2-bu ten es. To 12 (15.24 g, 60.5 mmol) in CH2Cl2 (300 mL)
was slowly added MCPBA (12.7 g, 58.9-62.5 mmol, 80-85%
assay) at 0 °C. The white suspension was stirred at 0 °C for
2 h, diluted with Et2O, washed with aqueous NaHCO3, 25%
aqueous sodium metabisulfite, and brine, dried (MgSO4),
filtered, and concentrated in vacuo. The resulting light yellow
liquid (16.2 g) on chromatography (silica gel; ethyl acetate:
hexanes, 1:5) gave 7 and 8 (15.87 g, 98%) as a viscous colorless
oil: IR (neat film) 1310, 1250, 1150 cm-1; 1H NMR (CDCl3, E-
and Z-isomers) δ -0.08 (s, 9 H), 1.24 (d, J ) 8.1 Hz, 2 H), 1.45
(d, J ) 8.1 Hz, 2 H), 3.74 (d, J ) 7.4 Hz, 2 H), 3.80 (d, J ) 7.4
Hz, 2 H), 5.10-5.35 (m, 1 H), 5.51-5.80 (m, 1 H), 7.52-7.86
(m, 5 H); 13C NMR (CDCl3, E- and Z-isomers) δ -2.1, -2.0,
20.8, 23.6, 54.9, 60.1, 112.5, 113.4, 128.2, 128.3, 128.9, 129.3,
Exp er im en ta l Section
Gen er a l Con sid er a tion s. Proton nuclear magnetic reso-
nance spectra are reported in parts per million on the δ scale
when CDCl3 is denoted as the solvent with residual CHCl3 at
δ 7.26 as an internal reference. The 1H NMR spectra are
reported as follows: chemical shifts [multiplicity (s ) singlet,
d ) doublet, t ) triplet, q ) quartet, m ) multiplet), coupling
constants in hertz, integration, and interpretation]. 13C NMR
chemical shifts are reported in parts per million relative to
the center line of the CDCl3 triplet (77.0 ppm) and are denoted
as “e” (none or two protons attached), “o” (one or three protons
attached), and “u” (quaternary carbon) as determined from the
APT pulse sequence and as “C” (no protons attached), “CH”
(one proton attached), “CH2” (two protons attached), or “CH3”
(three protons attached) as determined from the DEPT pulse
sequence. Mass spectra were recorded at an ionization energy
of 70 eV. THF was predried over potassium hydroxide and
distilled from lithium aluminum hydride, Et2O was distilled
from sodium benzophenone ketyl, and CH2Cl2 was distilled
from calcium hydride. All reactions were conducted under
argon. EM Laboratories 0.25 mm thick precoated silica gel
60F-254 plates were used for analytical chromatography.
Elemental analyses were performed by MicroAnalyses, Inc.,
Wilmington, DE, or Atlantic Microlab, Inc., Norcross, GA.
4-(Tr im eth ylsilyl)-1-bu ten -3-ol (10). (Chloromethyl)tri-
methylsilane (20.0 g, 0.163 mol) in anhydrous THF (30 mL)
was added in 2 h to a suspension of magnesium turnings (4.50
g, 0.205 mol) in anhydrous THF (120 mL). The mixture was
stirred at room temperature for 1 h and cooled to 0 °C.
Acrolein (9.50 g, 0.170 mol) in anhydrous THF (30 mL) was
then added (15 min), and the mixture was stirred for 45 min.
The solution was diluted with Et2O, quenched with hydro-
chloric acid, washed with water and brine, dried (MgSO4),
filtered, and concentrated in vacuo. The yellow liquid residue
(26.0 g) was distilled at 54-56 °C at 1.7 mmHg to give colorless
10 (16.2 g, 69%): 1H NMR (CDCl3) δ 0.02 (s, 9 H), 0.83-1.30
(m, 2 H), 2.05 (bs, 1 H), 4.25 (bq, J ) 7.2 Hz, 1 H), 5.01 (dd, J
) 7.8, 1.0 Hz, 1 H), 5.15 (dd, J ) 14.5, 1.3 Hz, 1 H), 5.82-5.92
(m, 1 H); 13C NMR (CDCl3) δ -0.8, 26.3, 71.5, 113.4, 143.4;
exact mass calcd for C7H16SiO m/e 144.0970, found m/e
144.0970.
133.4, 133.5, 135.6, 138.5; exact mass calcd for C7H15Si (M+
SO2Ph) m/e 127.0943, found m/e 127.0936.
-
(E,17)- a n d (Z,18)-1-Deu ter io-1-(p h en ylsu lfon yl)-4-(tr i-
m eth ylsilyl)-2-bu ten es. n-BuLi (0.21 mL, 0.56 mmol, 2.65
M) in hexane was added to a solution of 7 and 8 (80:20 ratio;
150 mg, 0.56 mmol) in THF (10 mL) at 0 °C. After being
stirred at 25 °C for 3.3 h, the mixture was quenched with D2O
(1 mL). The solution was immediately neutralized with
aqueous ammonium chloride, washed with H2O, dried (Mg-
SO4), filtered, and concentrated to a yellow clear oil (0.12 g).
Column filtration (silica gel; ethyl acetate 5%) yielded (E)-17
and (Z)-18 (71 mg, 47%): 1H NMR (CDCl3, E/Z isomer 79:21,
87% monodeuterium incorporation) δ -0.08 (s, 9 H), 1.25 (dd,
J ) 7.5, 1.4 Hz, 2 H), 1.46 (dd, J ) 8.2, 1.1 Hz, 2 H), 3.72 (bd,
J ) 7.2 Hz, 1 H), 5.18-5.26 (m, 1 H, Ha), 5.56 (dt, J ) 15.2,
8.2 Hz, 1 H, Hb), 5.76 (dt, J ) 10.7, 9.0 Hz, 1 H, Hb), 7.49-
7.91 (m, 5 H); 13C NMR (CDCl3, E/Z ratio 77:23 to 83:17) δ
-2.1, 18.9, 23.7, 60.0, 112.5, 129.0, 128.3, 128.4, 129.0, 133.4,
133.5, 135.8, 138.6, 138.8; mass spectrum, m/e calcd for C13H19
-
DO2SSi (M+) 269.1016, found 269.1005; C7H14DSi/C7H15Si (M+
- O2SPh) isotope ratio 84/16.
(E)- a n d (Z)-1,1-Did eu ter io-1-(p h en ylsu lfon yl)-4-(tr i-
m eth ylsilyl)-2-bu ten es (21 a n d 22). Products 21 and 22,
yield 89%, a light yellow liquid: 1H NMR (CCl4, >95%
deuterium incorporation) δ -0.00 (s, 9 H), 1.2-1.6 (m, 2 H),
5.18 (bd, J ) 15 Hz, 1 H), 5.32-5.97 (m with a dt at 5.62, J )
15.7 Hz, 1 H), 7.50-8.14 (m, 5 H); mass spectrum m/e calcd
for C7H12D2Si (M+ - O2SPh) 128.0990, found 128.1001.
P r oced u r e A for Mon osu bstitu tion Rea ction s of (E)-
a n d (Z)-1-(P h en ylsu lfon yl)-4-(tr im eth ylsilyl)-2-bu ten es
w ith Electr op h iles (7 a n d 8). (E)- a n d (Z)-4-(P h en ylsu l-
fon yl)-1-(tr im eth ylsilyl)-2-p en ten es (32a ). n-BuLi (3.51
mL, 7.38 mmol, 2.10 M in hexane) was syringed slowly into a
solution of 7 and 8 (1.80 g, 6.71 mmol) in anhydrous THF (10
mL) at -78 °C. The stirred mixture turned bright yellow.
After 20 min, methyl iodide (1.26 g, 8.88 mmol) was added.
The mixture was stirred for 1 h at room temperature, worked
up, and concentrated in vacuo to a yellow oil (1.39 g). Column
chromatography (silica gel; ethyl acetate:hexanes, 1:10) af-
forded 32a (1.84 g, 97%) as a colorless viscous liquid: 1H NMR
(CDCl3, E-isomer) δ 0.00 (s, 9 H), 1.35 (d, J ) 6.0 Hz, 3 H),
1.48 (m, 2 H), 3.59 (m, 1 H), 5.13 (dd, J ) 15.0, 7.0 Hz, 1 H),
5.58 (dt, J ) 15.0, 8.0 Hz, 1 H), 7.3-8.0 (m, 5 H); 13C NMR
(CDCl3, E-isomer) δ -2.0, 14.1, 23.6, 64.0, 120.8, 128.8, 129.1,
133.4, 135.6, 137.8; exact mass calcd for C8H17Si (M+ - SO2-
(E)- a n d (Z)-1-(P h en ylsu lfin yl)-4-(t r im et h ylsilyl)-2-
bu ten es (12). Phenylsulfenyl chloride (6.80 g, 47.1 mmol) was
added slowly to 10 (6.80 g, 47.1 mmol) and n-BuLi (30.6 mL,
49.0 mmol, 1.60 M in hexane) in anhydrous THF (50 mL) at
(14) (a) Lenihan, B. D.; Shechter, H. J . Org. Chem. 1998, 63, 2072.
(b) Lenihan, B. D.; Shechter, H. J . Org. Chem. 1998, 63, 2086.

(E)- and (Z)-1-(Phenylsulfonyl)-4-(trimethylsilyl)-2-butenes
Ph) m/e 141.1099, found m/e 141.1092. Anal. Calcd for
J . Org. Chem., Vol. 63, No. 13, 1998 4189
H), 4.13 (q, J ) 7.1 Hz, 2 H), 4.47 (d, J ) 9.5 Hz, 1 H), 5.27-
5.37 (m, 1 H), 5.74-5.86 (m, 1 H), 7.50-7.56 (m, 2 H), 7.59-
7.68 (m, 1 H), 7.84-7.87 (m, 2 H); 13C NMR (CDCl3, E- and
Z-isomers) δ -2.1, -2.0, 13.8, 23.7, 24.1, 60.3, 62.1, 74.6, 113.4,
114.3,128.3, 128.8, 129.0, 129.5, 133.4, 134.0, 137.4, 138.6,
142.8, 165.1; exact mass calcd for C10H19O2Si (M+ - SO2Ph)
m/e 199.1154, found m/e 199.1201. Anal. Calcd for C16H24O4-
SSi: C, 56.44; H, 7.10. Found: C, 56.79; H, 6.72.
C
14H22O2SSi: C, 59.52; H, 7.85. Found: C, 59.64; H, 7.55.
(E)- a n d (Z)-5-P h en yl-4-(p h en ylsu lfon yl)-1-(tr im eth yl-
silyl)-2-p en ten es (32b). Procedure A, yield 99%, a clear
viscous oil: 1H NMR (CDCl3, E-isomer) δ 0.09 (s, 9 H), 1.66
(m, 2 H), 3.16 (Ha, dd, J ab ) 13.6 Hz, J ) 11.6 Hz, 1 H), 3.85
(Hb, dd, J ab ) 13.5 Hz, J ) 3.0 Hz, 1 H), 4.06 (Hc, m, 1 H),
5.3-5.7 (m, 2 H), 7.4-8.3 (m, 10H); irradiation at δ 1.66
simplified the vinyl absorption region to 5.3-5.4 (m, 1 H) and
5.58 (d, J ) 14.9 Hz, 1 H); irradiation at δ 4.06 simplified the
vinyl and benzyl magnetic resonance regions to 5.38 (dd, J )
15.2, 4.3 Hz, 1 H) and 5.4-5.7 (m, 1 H) and 3.85 (d, J ) 15.2
Hz, 1 H); 13C NMR (CDCl3, E-isomer) δ -2.1, 23.7, 34.0, 71.0,
118.8, 126.7, 128.5, 128.9, 129.2, 133.5, 137.1, 138.0, 138.3;
exact mass calcd for C14H21Si (M+ - SO2Ph) m/e 217.1412,
found m/e 217.1407. Anal. Calcd for C20H26O2SSi: C, 66.99;
H, 7.31. Found: C, 67.03; H, 6.94.
Eth yl (E)- a n d (Z)-2-(P h en ylsu lfon yl)-5-(tr im eth ylsi-
lyl)-3-p en t en et h ioa t es (32 g). Procedure A, yield 45%, a
viscous liquid: 1H NMR (CDCl3, E- and Z-isomers) δ -0.08
(s, 9 H), -0.02 (s, 9 H), 1.17 (t, J ) 7.4 Hz, 3 H), 1.56 (d, J )
9.5 Hz, 2 H), 2.85 (q, J ) 7.4 Hz, 2 H), 4.56 (d, J ) 9.5 Hz, 1
H), 4.90 (d, J ) 9.5 Hz, 1 H), 5.27-5.40 (m, 1 H), 5.74-5.90
(m, 1 H), 7.47-7.68 (m, 3 H), 7.81-7.90 (m, 2 H); 13C NMR
(CDCl3, E- and Z-isomers) δ -2.0, -1.9, 14.2, 18.9, 19.7, 24.1,
24.2, 80.3, 112.5, 114.2, 128.3, 128.4, 128.7, 128.9, 129.6, 134.0,
135.7,140.6, 190.8; exact mass calcd for C8H14OSi (M+ - SO2-
Ph, SCH2CH3) m/e 154.0814, found m/e 154.0813. Anal. Calcd
for C16H24O3S2Si: C, 54.90; H, 6.78. Found: C, 54.69; H, 6.95.
(E)- a n d (Z)-2,2-Dim eth yl-4-(p h en ylsu lfon yl)-7-(tr im -
eth ylsilyl)-5-h ep ten -3- on es (32h ). Procedure A: (1) (E)-
32h (59%), a white solid [mp 99-100 °C; 1H NMR (CDCl3,
E-isomer) δ -0.03 (s, 9 H), 1.13 (s, 9 H), 1.50 (d, J ) 8.0 Hz,
2 H), 5.04-5.15 (m, 2 H), 5.73-5.85 (m, 1 H), 7.49-7.87 (m, 5
H); 13C NMR (CDCl3, E-isomer) δ -1.9, 24.0, 25.9, 45.8, 73.6,
117.0, 128.5, 130.2, 133.8, 137.6, 142.3, 206.2; exact mass calcd
for C12H23OSi (M+ - SO2Ph) m/e 211.1520, found m/e 211.1545.
Anal. Calcd for C20H28O3SSi: C, 61.32; H, 8.01. Found: C,
61.63; H, 8.01] and (2) (Z)-32h (16%), a colorless oil [1H NMR
(CDCl3, Z-isomer) δ 0.06 (s, 9 H), 1.16 (s, 9 H), 1.46-1.66 (m,
2 H), 5.02-5.07 (m, 1 H), 5.52 (d, J ) 10.1 Hz, 1 H), 5.77-
5.81 (m, 1 H), 7.48-7.84 (m, 5 H); 13C NMR (CDCl3, Z-isomer)
δ -1.5, 19.3, 26.0, 45.5, 68.5, 117.3, 128.4, 130.3, 133.8, 136.3,
137.5, 206.6; exact mass calcd for C12H23OSi (M+ - SO2Ph)
m/e 211.1520, found m/e 211.1541].
P r oced u r e B for Mon osu bstitu tion Rea ction s of 7 a n d
8 w ith Electr op h iles. (E)- a n d (Z)-4-(P h en ylsu lfon yl)-1-
(tr im eth ylsilyl)-2-n on en es (32c). n-BuLi (1.97 mL, 2.95
mmol, 1.50 M in hexane) was syringed into a solution of 7 and
8 (726 mg, 2.70 mmol) in anhydrous THF (20 mL). After 20
min, 1-bromopentane (429 mg, 2.84 mmol) followed by HMPA
(2.57 mL, 14.00 mmol) was added. After being warmed to
room temperature, the mixture was stirred for 1 h, worked
up, and concentrated to a yellow viscous oil (1.13 g). Column
chromatography (silica gel; ethyl acetate 0-5%) gave 32c (875
mg, 99%) as a light yellow oil: 1H NMR (CDCl3, E-isomer) δ
0.00 (s, 9 H), 0.7-2.2 (m with a δ, J ) 8.0 Hz at δ 1.46, 13 H),
3.30 (bt, J ) 9.0 Hz, 1 H), 4.95 (dd, J ) 15.0, 9.0 Hz, 1 H),
5.40 (dt, J ) 15.0, 8.0 Hz, 1 H), 7.3-8.0 (m, 5 H); 13C NMR
(CDCl3, E-isomer) δ -2.0, 13.9, 22.4, 23.7, 26.3, 27.4, 31.2, 69.6,
119.8, 128.8, 129.1, 133.3, 137.2, 138.3; exact mass calcd for
C
12H25Si (M+ - SO2Ph) m/e 197.1726, found m/e 197.1729.
(E)- a n d (Z)-6-Meth yl-4-(p h en ylsu lfon yl)-1-(tr im eth yl-
silyl)-2-h ep ten es (32d ). Procedure B, yield 83%, a colorless
viscous oil: 1H NMR (CDCl3, E-isomer) δ 0.00 (s, 9 H), 0.79
(d, J ) 6.5 Hz, 3 H), 0.94 (d, J ) 6.5 Hz, 3 H), 1.2-1.8 (m, 5
H), 3.53 (bt, J ) 9.3 Hz, 1 H), 4.99 (dd, J ) 15.2, 9.4 Hz, 1 H),
5.47 (dt, J ) 15.2, 9.1 Hz, 1 H), 7.5-7.9 (m, 5 H); 13C NMR
(CDCl3, E-isomer) δ -2.0, 20.5, 23.5, 25.2, 35.9, 68.1, 119.7,
(E)-1-P h en yl-2-(p h en ylsu lfon yl)-5-(t r im et h ylsilyl)-3-
p en ten -1-on e (32i). Procedure A, yield 64%, a viscous yellow
liquid: 1H NMR (CDCl3) δ -0.05 (s, 9 H), 1.54 (d, J ) 6.9 Hz,
2 H), 5.34-5.44 (m, 1 H), 5.56 (d, J ) 9.2 Hz, 1 H), 5.82-5.95
(m, 1 H), 7.29-7.66 (m, 6 H), 7.83-7.98 (m, 4 H); 13C NMR
(CDCl3) δ -1.9, 24.2, 74.4, 115.8, 117.3, 127.6, 128.5, 128.6,
128.7, 128.9, 129.1, 130.0, 133.9, 133.9, 136.1, 137.2 142.9,
191.3; exact mass calcd for C14H19OSi (M+ - SO2Ph) m/e
231.1206, found m/e 231.1214. Anal. Calcd for C20H24O3SSi:
C, 64.48; H, 6.49. Found: C, 64.65; H, 6.25.
128.7, 129.0, 133.2, 137.1, 138.1; exact mass calcd for C11H23
-
Si (M+ - SO2Ph) m/e 183.1569, found m/e 183.1592.
(E)- a n d (Z)-5-Meth yl-4-(p h en ylsu lfon yl)-1-(tr im eth yl-
silyl)-2-h exen es (32e). Procedure B, yield 97%, a colorless
oil: 1H NMR (CDCl3, E-isomer) δ -0.07 (s, 9 H), 0.95 (d, J )
7.0 Hz, 3 H), 1.08 (d, J ) 7.0 Hz, 3 H), 1.35-1.52 (m, 2 H),
2.65 (m, 1 H), 3.30 (m, 1 H), 5.27 (m, 2 H), 7.4-7.8 (m, 5 H);
13C NMR (CDCl3, E-isomer) δ -2.0, 18.0, 22.0, 23.7, 26.9, 74.9,
116.5, 128.7 (2 coincidental peaks), 133.1, 138.1, 139.3; exact
mass calcd for C10H21Si (M+ - SO2Ph) m/e 169.1413, found
m/e 169.1392. Anal. Calcd for C16H26O2SSi: C, 61.89; H, 8.44.
Found: C, 61.39; H, 8.23.
(E)- a n d (Z)-2-(1-(P h en ylsu lfon yl)-4-(tr im eth ylsilyl)-2-
bu ten -1-yl)cycloh exa n ols (32j). Procedure A, column chro-
matography of the reaction product gave 32j (83%), a partially
resolved mixture of diastereomers (two by TLC). The more
polar isomer was obtained as a colorless oil which crystallized
to a white solid: mp 122-123 °C; 1H NMR (CDCl3, polar
isomer) δ -0.13 (s, 9 H), 1.21-2.33 (m, 11 H), 3.17 (m, 1 H),
4.17 (dd, J ) 9.4, 2.1 Hz, 1 H), 5.3-5.4 (m, 2 H), 7.34-7.95
(m, 5 H); 13C NMR (CDCl3, polar isomer) δ -2.0, 23.7, 24.9,
25.2, 26.4, 36.4, 44.2, 68.5, 70.6, 116.4, 128.6, 128.7, 133.1,
138.2, 139.0; mass spectrum (polar isomer), m/e calcd for
(E)- a n d (Z)-5-Meth yl-6-p h en yl-4-(p h en ylsu lfon yl)-1-
(tr im eth ylsilyl)-2-h exen es (33 a n d 34). Procedure B: col-
umn chromatography gives as the first eluent (E)-1-phenyl-
1
1-propene (25%) and initial bromide as assigned by H NMR
and GLC analyses (column QF-1, 15%, Chromosorb W). The
second eluent is (E)-33 and (Z)-34 (40%), an unresolved
mixture of diastereomers as a colorless oil. The 1H NMR of
the mixture could not be assigned because of the ambiguous
coupling patterns; mass spectrum, m/e calcd for C16H25Si (M+
- O2SPh) 245.1725, found 245.172. GC-Cl-MS (isobutane) of
the product revealed three isomers, A,B, and C, in a ratio of
54:42:4: isomer A, m/e (relative intensity) 387 (0.4, M+ + H),
287 (5), 245 (31), 215 (100), 173 (8), 143 (38), 126 (11), 105 (6),
91 (6), 73 (5); isomer B, 387 (0.4 M+ + H), 287 (19), 245 (24),
215 (100), 173 (7), 143 (33), 126 (7), 105 (5), 91 (4), 73 (5);
isomer C, 387 (1, M+ + H), 287 (100), 245 (5), 215 (22), 173
(1), 143 (1). Last, 7 and 8 (33% recovery) were eluted from
the column.
C
13H26OSi (M+ - O2SPh) 226.1753, found 226.1720.
(E)- a n d (Z)-4-(P h en ylsu lfon yl)-7-(t r im et h ylsilyl)-5-
h ep ten -2-ols (32k ). Procedure A, yield 59%, a yellow oil: 1H
NMR (CDCl3) δ -0.11 (s, 9 H), 1.14, 1.21 (d, J ) 6.2 Hz, 3 H),
1.32-1.50 (m, 2 H), 1.6-1.9 (m, 1 H), 2.02-2.20 (m, 2 H), 3.6-
4.1 (m, 1 H), 4.9-5.1 (m, 1 H), 5.40-5.58 (m, 1 H), 7.40-7.85
(m, 5 H); 13C NMR (CDCl3) δ -2.0, 22.7, 23.6, 24.3, 64.5, 65.5,
66.5, 66.7, 119.0, 119.9, 128.8, 128.8, 129.0, 133.3, 133.4, 137.3,
137.5, 137.8; exact mass calcd for C10H21OSi (M+ - SO2Ph)
m/e 205.1362, found m/e 205.1349. Anal. Calcd for C16H26O3-
SSi: C, 58.85; H, 8.03. Found: C, 58.57; H, 7.63.
(E)- a n d (Z)-5-(P h en ylsu lfon yl)-8-(t r im et h ylsilyl)-6-
octen -3-ols (32l). Procedure A, yield 52%, a yellow viscous
oil: 1H NMR (CDCl3) δ -0.12 (s, 9 H), 0.88 (t, J ) 7.4 Hz, 3
H), 1.32-1.55 (m, 4 H), 1.64-1.82 (m, 1 H), 2.0-2.3 (m, 2 H),
3.38-3.50 (m), 3.68-3.94 (m, 1 H), 4.95-5.12 (m, 1 H), 5.38-
5.55 (m, 1 H), 7.40-7.85 (m, 5 H); 13C NMR (CDCl3) δ -2.0,
-1.9, 9.5, 9.8, 23.5, 23.6, 29.4, 31.0, 34.4, 35.6, 66.4, 66.5, 69.7,
Eth yl (E)- a n d (Z)-2-(P h en ylsu lfon yl)-5-(tr im eth ylsi-
lyl)-3-p en ten oa tes (32f). Procedure A, yield 67%, liquid: 1H
NMR (CDCl3, E- and Z-isomers) δ -0.01 (s, 9 H), 1.20 (t, J )
7.1 Hz, 3 H), 1.46 (d, J ) 8.0 Hz, 2 H), 1.55 (d, J ) 7.4 Hz, 2

4190 J . Org. Chem., Vol. 63, No. 13, 1998
Meagher et al.
70.5, 119.1, 120.2, 128.7, 128.8, 129.0, 129.1, 133.3, 133.4,
137.1, 137.8; exact mass calcd for C11H23OSi (M+ - SO2Ph)
m/e 199.1520, found m/e 199.1528. Anal. Calcd for C17H28O3-
SSi: C, 59.96; H, 8.29. Found: C, 59.52; H, 8.08.
trated in vacuo to a brown oil (140 mg). Column chromatog-
raphy (silica gel; ethyl acetate:hexanes, 1:5) afforded 38b (65
mg, 52%): 1H NMR (CDCl3) δ 3.42 (d, J ) 6.9 Hz, 2 H), 4.99
(Ha, dd, J ) 9.4, 1.2 Hz, 1 H), 5.12 (Hb, dd, J ) 16.5, 1.5 Hz,
1 H), 5.84 (Hc, dt, J ) 15.1, 7.0 Hz, 1 H), 6.10 (Hd, dd, J )
15.1, 10.2 Hz, 1 H), 6.33 (He, ddd, J ) 16.8, 10.1 Hz, 1 H). The
(E)- a n d (Z)-1-P h en yl-3-(p h en ylsu lfon yl)-6-(tr im eth yl-
silyl)-4-h exen -1-ols (32m ). Procedure A, yield 54%, a viscous
yellow liquid: 1H NMR (CDCl3) δ -0.05 (s, 9 H), 1.42-1.52
(m, 2 H), 2.15 (s, 1 H), 2.40-2.51 (m, 2 H), 3.40-3.49 (m, 1
H), 4.81 (t, J ) 7.1 Hz, 1 H), 5.02-5.16 (m, 1 H), 5.36-5.70
(m, 1 H), 7.23-7.94 (m, 10H); 13C NMR (CDCl3) δ -2.2, -1.9,
23.7, 37.2, 66.1, 66.6, 70.7, 71.8, 119.4, 120.8, 125.6, 126.0,
127.9, 128.1, 128.4, 128.6, 128.7, 128.8, 129.0, 133.4, 137.4,
137.7, 138.3, 142.5; exact mass calcd for C15H23OSi (M+ - SO2-
Ph) m/e 247.1520, found m/e 47.1503.
1
IR and H NMR spectra of 38b agree with literature values.15a
KF /Cetyltr im eth yla m m on iu m Br om id e Meth od ology
for Elim in a tin g 32b to (E)-5-P h en yl-1,3-p en ta d ien e (38b).
A solution of 32b (272 mg, 0.76 mmol), potassium fluoride (170
mg, 3.0 mmol), and cetyltrimethylammonium bromide (40 mg,
0.11 mmol) in acetonitrile (10 mL) was refluxed for 16 h.
VPLC analysis using (E)-propenylbenzene as an internal
standard showed 38b to be produced in 63% yield.
(E)- a n d (Z)-1-(P h en ylsu lfon yl)-1-(tr ieth ylger m a n yl)-
4-(tr im eth ylsilyl)-2-bu ten es (32n ). Procedure B, yield 35%,
a colorless oil: 1H NMR (CDCl3, E- and Z-isomers) δ -0.28 (s,
9 H), -0.17 (s, 9 H), 1.09-1.14 (m, 15 H), 1.31-1.37 (m, 2 H),
3.51 (d, J ) 10.8 Hz, 1 H), 3.84 (d, J ) 11.0 Hz, 1 H), 5.01-
5.10 (m, 1 H), 5.22-5.34 (m, 1 H), 5.35-5.46 (m, 1 H), 7.42-
7.55 (m, 3 H), 7.75-7.80 (m, 2 H); 13C NMR (CDCl3, E- and
Z-isomers) δ -2.0, 5.2, 5.3, 8.8, 8.9, 17.9, 23.1, 56.1, 60.9, 119.2,
127.8, 128.0, 128.5, 128.6, 129.2, 132.4, 132.4, 132.5, 140.1,
141.0; exact mass calcd for C19H34SO2SiGe m/e 428.1261, found
m/e 428.1241. Anal. Calcd for C19H34SO2SiGe: C, 54.42; H,
8.02. Found: C, 54.61; H, 8.03.
(E)- a n d (Z)-6-Meth yl-1,3-h ep ta d ien es (38d ). Procedure
D, yield 63%, a colorless liquid: 1H NMR (CDCl3) δ 0.83 (d, J
) 6.6 Hz, 6 H), 1.59 (m, 1 H), 1.90 (dd, J ) 6.9 Hz, 2 H), 4.89
(Ha, dd, J ) 10.0, 0.50 Hz, 1 H), 5.00 (Hb, dd, J ) 16.7, 0.5 Hz,
1 H), 5.58 (Hc, dt, J ) 15.1, 7.4 Hz, 1 H), 5.95 (Hd, dd, J )
15.0, 10.3 Hz, 1 H), 6.23 (He, ddd, J ) 16.9, 10.2, 10.1 Hz, 1
H). Irradiation at δ 1.50 caused δ 5.58 to collapse to a doublet,
J ) 15.0 Hz; GC-MS detected two isomers in a 93:7 ratio
[major isomer m/e (relative intensity 110 (38, M+), 95 (21), 81
(10), 67 (89) 56 (61), 54 (65), 43 (99), 41 (100), 39 (50); minor
isomer m/e (relative intensity) 110 (37), 95 (38), 81 (7), 67 (93),
56 (57), 54 (59), 43 (89), 41 (100), 39 (59)].
(E)- a n d (Z)-1-(P h en ylsu lfon yl)-1,4-bis(tr im eth ylsilyl)-
2-bu ten es (32o). Procedure A, yield 51%, a yellow viscous
oil: 1H NMR (CDCl3, E- and Z-isomers) δ -0.27 (s, 9 H), -0.19
(s, 9 H), 0.28 (s, 9 H), 1.31 (m, 2 H), 3.32 (bd, J ) 10.3 Hz, 1
H), 3.68 (bd, J ) 10.7 Hz, 1 H), 5.02-5.42 (m, 2 H), 7.45-7.80
(m, 5 H); 13C NMR (CDCl3, E and Z-isomers) δ -2.1, -2.0,
-1.3, -1.1, 20.0, 23.2, 57.8, 63.0, 120.3, 127.8, 128.1, 128.5,
128.9, 130.6, 130.8, 132.5, 132.6, 133.8, 140.7, 140.8; exact
mass calcd for C16H28O2SSi2 m/e 340.1349, found m/e 340.1303.
Anal. Calcd for C16H28O2SSi2: C, 56.42; H, 8.29. Found: C,
56.57; H, 7.89.
(E)-1-(P h en ylsu lfon yl)-4-(tr im eth ylsilyl)-1-[tr i(2-pr opyl)-
silyl]-2-bu ten e (32p ). Procedure A, yield 33%, an off-white
solid: mp 101-102 °C: 1H NMR (CDCl3) δ -0.15 (s, 9 H), 1.19
(dd, J ) 15.6, 7.4 Hz, 18 H), 1.26-1.54 (m, 5 H), 3.61 (d, J )
11.0 Hz, 1 H), 4.82-4.95 (m, 1 H), 5.35-5.46 (m, 1 H), 7.43-
7.57 (m, 3 H), 7.75-7.83 (m, 2 H); 13C NMR (CDCl3) δ -1.9,
12.2, 20.9, 23.3, 60.2, 119.5, 128.0, 128.5, 132.4, 134.3, 140.8;
exact mass calcd for C22H40O2SSi2 m/e 424.2287, found m/e
424.2251. Anal. Calcd for C22H40O2SSi2: C, 62.21; H, 9.49.
Found: C, 61.87; H, 9.51.
(E)- a n d (Z)-4-Cycloh exyl-4-(p h en ylsu lfon yl)-1-(t r i-
m eth ylsilyl)-2-bu ten es (35). Procedure B, yield 35%, a clear
oil: 1H NMR (CDCl3, E-isomer) δ -0.08 (s, 9 H), 1.03-1.76
(m, 11 H), 2.12 (bd, J ) 12.7 Hz, 1 H), 2.35 (m, 1 H), 3.31 (dd,
J ) 9.8, 3.2 Hz, 1 H), 5.19-5.32 (m, 2 H), 7.31-7.81 (m, 5 H);
13C NMR (CDCl3, E-isomer) δ -1.9, 23.6, 26.0, 26.4, 28.6, 32.1,
36.7, 74.9, 117.4, 128.7, 133.0, 137.4, 139.1; exact mass calcd
for C13H25Si (M+ - SO2Ph) m/e 209.1726, found m/e 209.1720.
Reactants 7 and 8 (30%) were also recovered.
(E)-1-Cycloh exyl-1,3-bu ta d ien e (36). Procedure D, yield
57%: 1H NMR (CDCl3) δ 1.10-2.11 (m, 11 H, ring), 5.03 (Ha,
dd, J ) 15.3, 6.8 Hz, 1 H), 5.18 (Hb, dd, J ) 16.8, 0.6 Hz, 1 H),
5.75 (Hc, dd, J ) 15.3, 6.8 Hz, 1 H), 6.11 (Hd, dd, J ) 15.3,
10.2 Hz, 1 H), 6.40 (He, ddd, J ) 16.9, 10.2, 10.1 Hz, 1 H). The
1
IR and H NMR spectra of 36 correspond to the literature.15b
KF /TDA-1 Meth od ology for Elim in a tion . (E)-1-Cyclo-
h exyl-1,3-bu ta d ien e (36). A solution of 35 (270 mg, 0.77
mmol), anhydrous KF (134 mg, 2.31 mmol), and TDA-1 (30
mg, 0.09 mmol) in acetonitrile (10 mL) was refluxed for 20 h.
VPLC analysis revealed that 36 is formed in 65% yield.
E t h yl (E)-2,4-P en t a d ien oa t e (38f). Procedure D, yield
51%, a light yellow oil: 1H NMR (CDCl3) δ 1.29 (t, J ) 7.3 Hz,
3 H), 4.24 (q, J ) 7.2 Hz, 2 H), 5.48 (Ha, dd, J ) 10.5, 0.6 Hz,
1 H), 5.60 (Hb, dd, J ) 16.9, 0.6 Hz, 1 H), 5.91 (Hc, d, J ) 15.4
Hz, 1 H), 6.45 (Hd, ddd, J ) 17.5, 10.3 Hz, 1 H), 7.26 (He, dd,
J ) 15.5, 4.0 Hz, 1 H); 13C NMR (CDCl3) δ 14.3, 60.4, 122.3,
125.4, 134.8, 144.6, 166.8; exact mass calcd for C7H10O2 m/e
126.0681, found m/e 126.0717. The spectra of 38f correspond
to reported values.15c
(E)-2,2-Dim eth yl-4,6-h ep ta d ien -3-on e (38h ). Procedure
D, yield 74%, a yellow oil: 1H NMR (CDCl3) δ 1.16 (s, 9 H),
5.51 (Ha, dd, J ) 9.4, 0.6 Hz, 1 H), 5.64 (Hb, dd, J ) 15.5, 0.7
Hz, 1 H), 6.46 (Hc, ddd, J ) 17.6, 9.2, 7.7 Hz, 1 H), 6.57 (Hd,
d, J ) 14.3 Hz, 1 H), 7.26 (He, dd, J ) 15.8, 11.0 Hz, 1 H); 13
C
NMR (CDCl3) δ 26.2, 43.0, 124.9, 125.9, 135.3, 142.8, 204.4;
exact mass calcd for C9H14O m/e 138.1045, found m/e 138.1048.
The above spectra agree with that reported.15d
(E)-1-(1,3-Bu ta d ien yl)cycloh exa n -2-ol (38j).15e Proce-
dure D, yield 83%, a clear colorless oil: 1H NMR (CDCl3) δ
1.14-1.34 (m, 4 H), 1.64-2.05 (m, 5 H), 3.20-3.30 (m, 1 H),
5.02 (Ha, dd, J ) 9.8, 1.4 Hz, 1 H), 5.14 (Hb, dd, J ) 17.0, 1.1
Hz, 1 H), 5.57 (Hc, dd, J ) 15.1, 8.6 Hz, 1 H), 6.17 (Hd, dd, J
) 15.0, 10.3 Hz, 1 H), 6.32 (He, ddd, J ) 16.5, 10.5, 9.8 Hz, 1
H); 13C NMR (CDCl3) δ 24.7, 25.1, 31.2, 34.0, 49.9, 73.2, 116.1,
132.7, 136.5, 136.8; exact mass calcd for C10H16O m/e 152.1201,
found m/e 152.1188. The spectral data for 38j are similar to
that recorded.
Procedure B with cyclohexyl p-toluenesulfonate at room
temperature led to 35 (27% conversion).
Gen er a l P r oced u r e C for F lu or id e-In d u ced Elim in a -
tion s of Silyl Su lfon es in DMSO. (E)- a n d (Z)-1,3-P en -
ta d ien es (38a ). DMSO (7 mL) was added to TBAF (7.08 mL,
7.08 mmol, 1.0 M in THF), and the mixture was concentrated
(0.1 mmHg/25 °C). The TBAF/DMSO reagent was then added
to 32a (1.08 g, 3.82 mmol) in DMSO (5 mL) at 25 °C. After
being stirred for 20 min, the mixture was flash distilled (15
°C/30-100 mmHg). The volatile components were trapped at
-78 °C to give a mixture of 38a (197 mg, 76%) and hexa-
methyldisiloxane (213 mg). The IR and 1H NMR of 38a are
essentially identical to that of an authentic sample.
Gen er a l P r oced u r e D for F lu or id e-In d u ced Elim in a -
tion s of 1-(P h en ylsu lfon yl)-1-su bstitu ted -4-(tr im eth yl-
silyl)-2-bu ten es (32). (E)-5-P h en yl-1,3-p en ta d ien e (38b).
TBAF (1.74 mL, 1.74 mmol, 1.0 M in THF) was added to 32b
(313 mg, 0.870 mmol) in anhydrous THF (10 mL) at 0 °C. The
dark mixture was stirred for 30 min, worked up, and concen-
(E)-4,6-Hep ta d ien -2-ol (38k ).15f Procedure D, yield 76%,
a viscous yellow oil: 1H NMR (CDCl3) δ 1.20 (d, J ) 6.2 Hz, 3
(15) (a) Hsiao, C.-N. Ph.D. Dissertation, The Ohio State University,
Columbus, OH, 1982. (b) Chan, T. H. Tetrahedron Lett. 1978, 2383.
(c) Bloch, R.; Abecassis, J .; Hassan D. Can. J . Chem. 1984, 62, 2019.
(d) Seebach, D.; Pohmakotr, M. Tetrahedron 1981, 37, 4047. (E)
Wender, P. A.; Sieburth, S. M.; Petratis I. I.; Singh. S. Tetrahedron
1981, 37, 3967. (f) Seyferth, D.; Pornet, J . J . Org. Chem. 1980, 45,
1721. (g) Corey, E. J .; Cane, D. E. J . Org. Chem. 1969, 34, 3053. (h)
Booker, H.; Evans, L. K.; Gillam, A. E. J . Chem. Soc. 1940, 1462.

(E)- and (Z)-1-(Phenylsulfonyl)-4-(trimethylsilyl)-2-butenes
J . Org. Chem., Vol. 63, No. 13, 1998 4191
H), 1.88 (bs, 1 H), 2.12-2.21 (m, 2 H), 3.76-3.86 (m, 1 H),
4.99 (Ha, dd, J ) 10.2, 1.7 Hz, 1 H), 5.11 (Hb, dd, J ) 16.3, 1.7
Hz, 1 H), 5.61-5.73 (Hc, m, 1 H), 6.11 (Hd, dd, J ) 15.1, 10.6
Hz, 1 H), 6.29 (He, ddd, J ) 16.8, 10.2, 10.1 Hz, 1 H); 13C NMR
(CDCl3) δ 22.8, 42.4, 67.3, 116.0, 130.5, 134.1, 136.8; exact
mass calcd for C7H12O m/e 112.0888, found m/e 112.0911.
(E)-1-P h en yl-3,5-h exadien -1-ol (38m ). Procedure D, yield
57%, a liquid: 1H NMR (CDCl3) δ 2.09 (bs, 1 H), 2.54 (t, J )
7.1 Hz, 2 H), 4.74 (t, J ) 6.6 Hz, 1 H), 5.03 (Ha, dd, J ) 8.6,
1.7 Hz, 1 H), 5.15 (Hb, dd, J ) 15.8, 1.7 Hz, 1 H), 5.62-5.74
(Hc, m, 1 H), 6.15 (Hd, dd, J ) 14.8, 10.5 Hz, 1 H), 6.32 (He,
ddd, J ) 16.7, 10.2, 10.2 Hz, 1 H), 7.28-7.41 (m, 5 H); 13C
NMR (CDCl3) δ 42.6, 73.6, 116.2, 125.8, 127.6, 128.4, 130.1,
134.4, 136.7, 143.8; exact mass calcd for C12H14O m/e 174.1045,
found m/e 174.1091. The spectra agree with published data.15h
(E)-1-[Tr i(2-p r op yl)silyl]-1,3-bu ta d ien e (38p ). Proce-
dure D, yield 61%, a colorless oil: 1H NMR (CDCl3) δ 1.01-
1.11 (m, 21 H), 5.10 (Ha, dd, J ) 9.8, 1.6 Hz, 1 H), 5.21 (Hb,
dd, J ) 16.8, 1.6 Hz, 1 H), 5.79 (Hc, d, J ) 20.5 Hz, 1 H), 6.36
(Hd, ddd, J ) 16.6, 9.6, 9.4 Hz, 1 H), 6.58 (He, dd, J ) 20.5, 9.9
Hz, 1 H); 13C NMR (CDCl3) δ 10.9, 20.6, 117.0, 129.3, 140.3,
146.7; exact mass calcd for C13H26Si m/e 210.2004, found m/e
210.1780.
(E)- a n d (Z)-5-Met h yl-6-p h en yl-1,3-h exa d ien es (38q).
Procedure D, yield 78%, a colorless oil: 1H NMR (CDCl3) δ
1.01 (d, J ) 4.5 Hz, 3 H), 2.43-2.75 (m, 3 H), 4.95 (Ha, dd, J
) 10.0, 1.7 Hz, 1 H), 5.07 (Hb, dd, J ) 16.9, 1.7 Hz, 1 H), 5.67
(Hc, dd, J ) 15.3, 6.4 Hz, 1 H), 5.99 (Hd, dd, J ) 15.4, 10.4 Hz,
1 H), 6.28 (He, ddd, J ) 17.1, 10.2, 10.1 Hz, 1 H), 7.10-7.35
(m, 5 H); 13C NMR (CDCl3) δ 19.5, 38.3, 43.4, 115.1, 125.9,
128.1, 128.2, 129.3, 137.4, 140.2, 140.5; mass spectrum, m/e
calcd for C13H16(M+) 172.1259; GC-MS detected two isomers
in a ratio of 96:4 [major isomer m/e (relative intensity) 172
(8), 143 (5), 91 (44), 81 (100), 65 (15), 53 (15), 41 (18), 39 (15);
minor isomer m/e (relative intensity) 172 (15), 143 (100), 128
(86), 115 (38), 91 (30), 77 (10), 65 (13), 51 (11), 39 (23)].
Sin gle-P ot Dia lk yla tion s of (E)- a n d (Z)-1-(P h en ylsu l-
fon yl)-4-(tr im eth ylsilyl)-2-bu ten es. (E)- a n d (Z)-4-Meth -
yl-4-(p h en ylsu lfon yl)-1-(tr im eth ylsilyl)-2-p en ten es (47).
n-BuLi (0.22 mL, 0.35 mmol, 1.60 M in hexane) was added to
7 and 8 (83 mg, 0.31 mmol) at -78 °C in THF (10 mL). After
20 min, methyl iodide (91 mg, 0.64 mmol) was added. The
mixture was warmed to -30 °C and recooled to -78 °C, and
additional n-BuLi (0.30 mL, 0.48 mmol, 1.60 M) was added.
The solution was stirred for 15 min, and more methyl iodide
(68 mg, 0.48 mmol) was added. The mixture was warmed to
∼20 °C, stirred for 1 h, taken up in Et2O, worked up, and
concentrated. Column chromatography (silica gel; ethyl ac-
etate 0-5%) of the concentrate gave (E,Z)-47 (93 mg, 98%), a
colorless viscous oil: 1H NMR (CDCl3) δ 0.00 (s, 9 H), 1.2-1.7
(m with a singlet at δ 1.33; 8 H), 5.2-5.7 (m, 2 H), 7.3-8.0
(m, 5 H); mass spectrum, m/e calcd for C9H19Si (M+ - O2SPh)
155.1256, found 155.1244.
E-isomer) δ 0.00 (s, 9 H), 1.52 (d, J ) 8 Hz, 2 H), 3.25 (s, 4 H),
5.28 (d, J ) 17 Hz, 1 H), 5.78 (dt, J ) 17.8 Hz, 1 H), 7.1-8.0
(m, 15 H); mass spectrum, m/e calcd for C20H25O2SSi (M+
-
C7H7) 357.1344, found 357.1304.
(E)- a n d (Z)-4-Ben zyl-5-p h en yl-4-(p h en ylsu lfon yl)-1-
(tr im eth ylsilyl)-2-n on en es (50) a n d (E)- a n d (Z)-4-Ben zyl-
1,3-n on a d ien es (51). Procedure E, (E,Z)-50, yield 61%, a
clear oil [1H NMR (CCl4, E-isomer) δ 0.07 (s, 9 H), 0.81-1.86
(m, 13 H), 3.18 (Ha, d, J ) 13.8 Hz, 1 H) 3.44 (Hb, J ) 13.9 Hz,
1 H), 5.27 (d, J ) 15.8 Hz, 1 H), 5.42 (dt, J ) 15.8, 7.8 Hz, 1
H), 7.1-7.9 (m, 10 H); 13C NMR (CDCl3, E-isomer) δ 1.8 (o),
13.9 (o), 22.3 (e), 23.6 (e), 23.9 (e), 31.0 (e), 32.5 (e), 36.6 (e),
71.8 (u), 125.3 (o), 135.6 (u), 136.6 (o), 128.2 (o), 130.6 (o), 130.6
(o), 133.2 (o), 134.0 (o), 135.7 (u), 136.6 (u), mass spectrum,
m/e calcd for C19H31Si (M+ - O2SPh) 287.2195, found 287.2200]
and (E,Z)-51 (yield 30%, E/Z ) 54:46) as a clear colorless oil
[IR (neat film) 1600 cm-1; NOE differences with irradiation
at δ 5.88 gave enhancements at δ 3.39 (4.85%), 5.13 (5.18%),
6.61 (1.82%), and 7.1-7.2 (2.24%); NOE differences with
irradiation at δ 6.05 resulted in enhancements at δ 1.99
(4.32%), 5.21 (5.55%), and 6.74 (1.54%); mass spectrum, m/e
calcd for
C
16H22 (M+) 214.1722, found 214.1744; GC-MS
detected two isomers in a 54:46 ratio [major isomer m/e
(relative intensity) 214 (30, M+), 171 (1), 157 (17), 143 (100),
129 (40), 128 (28), 115 (18), 91 (67), 81 (16), 79 (10), 77 (9), 67
(18), 65 (14); minor isomer m/e (relative intensity) 214 (29, M+),
171 (1), 157 (18), 143 (100), 129 (39), 128 (28), 115 (18), 91
(62), 81 (14), 79 (9), 67 (17), 65 (13)]].
Elim in a tion of (E)- a n d (Z)-4-Ben zyl-4-(p h en ylsu lfo-
n yl)-1-(tr im eth ylsilyl)-2-n on en es (50) on Silica Gel. De-
benzenesulfonyltrimethylsilylation of (E,Z)-50 (127 mg, 0.30
mmol) was effected on silica gel (pentane). After 0.5 h, the
column was eluted with pentane and evaporated to yield (E,Z)-
51 (27 mg, 42%).
(E)- a n d (Z)-4-Meth yl-5-p h en yl-1,3-p en ta d ien es (56).
Procedure D, yield 75%, an oil: 1H NMR (CDCl3, E- and
Z-isomers) δ 1.53 (s, 3 H, Z), 1.70 (s, 3 H, E), 3.35 (s, 2 H, E),
3.50 (s, 2 H, Z), 5.01-5.06 (Ha, two overlapping dd, J E ) 10.2,
1.7 Hz, E and Z), 5.13 (Hb, dd, J ) 16.8, 1.9 Hz, 1 H, E), 5.18
(Hb, d, J ) 16.7, Hz, 1 H, Z), 5.93 (Hc, d, J ) 10.5 Hz, 1 H, E),
6.01 (Hc, d, J ) 10.6 Hz, 1 H, Z), 6.57 (Hd, ddd, J ) 16.8, 10.5
Hz, 1 H, E), 6.72 (Hd, ddd, J ) 16.8, 10.5, 10.5 Hz, 1 H, Z),
7.1-7.4 (m, 5 H); NOE differences with irradiation at δ 5.93
gave enhancements at 3.35 (2.93%) and 5.13 (2.53%); 13C NMR
(CDCl3, E and Z-isomers) δ 16.5 (o, Z), 23.5 (o, Z), 38.3 (e, Z),
46.2 (e, E), 115.5 (e, E), 115.6 (e, Z), 126.1 (o, Z), 126.1 (o, E),
127.1 (o, E), 127.5 (o, Z), 128.3 (o, E), 128.4 (o, Z), 128.6 (o, Z),
129.0 (o, E), 133.1 (o, Z), 133.4 (o, E), 138.0 (u, Z), 138.4 (u,
E), 139.6 (u, E); mass spectrum, m/e calcd for C12H14 (M+)
158.1095, found 158.1095. GC-MS detected two isomers in a
80:20 ratio [major isomer m/e (relative intensity) 158 (46), 143
(100), 129 (56), 128 (75), 115 (38), 103 (5), 91 (53), 80 (12), 79
(15), 77 (18), 65 (39), 63 (16), 51 (24).
P r oced u r e E for Mon oa lk yla tion of (E)- a n d (Z)-1-
(P h en ylsu lfon yl)-1-su b st it u t ed -4-(t r im et h ylsilyl)-2-b u -
ten es (32); (E)- a n d (Z)-4-Meth yl-5-p h en yl-4-(p h en ylsu l-
fon yl)-1-(tr im eth ylsilyl)-2-p en ten es (48). n-BuLi (0.23 mL,
0.53 mmol, 2.30 M) was added to a solution of 32b (170 mg,
0.48 mmol) in THF (10 mL) at -78 °C. Methyl iodide (136
mg, 0.96 mmol) was added after 20 min. The solution was
then stirred 1 h at room temperature, diluted with Et2O,
worked up, and concentrated to a yellow mobile oil, 211 mg.
Column chromatography (silica gel; ethyl acetate 0-3%)
yielded (E,Z)-48 (170 mg, 97%): 1H NMR (CDCl3, E-isomer) δ
-0.12 (s, 9 H), 1.21 (s, 3 H), 1.46 (m, 2 H), 3.17 (Ha, d, J )
12.9 Hz, 1 H), 3.29 (Hb, d, J ) 13.0 Hz, 1 H), 5.19 (dt, J )
15.6, 7.5 Hz, 1 H), 5.53 (dt, J ) 15.6 Hz, 1.2 Hz, 1 H), 7.0-7.3
(m, 5 H), 7.4-7.9 (m, 5 H); 13C NMR (CDCl3, E-isomer) δ -1.8
(q), 17.1 (e), 23.7 (t), 39.5 (t), 69.0 (s), 124.3 (d), 126.7 (d), 127.9
(d), 128.3 (d), 130.7 (d), 130.8 (d), 133.3 (d), 134.6 (d), 135.2
(s), 135.7 (s); mass spectrum, m/e calcd for C15H23Si (M+ - O2-
SPh) 231.1569, found 231.1590.
(E)- a n d (Z)-1-(P h en ylsu lfon yl)-1-(3-(tr im eth ylsilyl)-1-
p r op en yl)cyclop r op a n es (62) a n d (E)- a n d (Z)-1-(P h en -
ylsu lfon yl)-1-(3-(tr im eth ylsilyl)-1-p r op en yl)tetr a h yd r o-
p yr a n s (66). A solution was prepared from 7 and 8 (509 mg,
1.89 mmol) and n-BuLi (0.79 mL, 2.09 mmol, 2.65 M in hexane)
in Et2O (10 mL) at -78 °C. Excess ethylene oxide (66, 1.13 g,
25.67 mmol) was added. The mixture was refluxed for 1.3 h
and then cooled to 0 °C. Methanesulfonyl chloride (0.22 g, 1.90
mmol) was added. The solution was refluxed for 1.5 h and
then cooled to -78 °C. More n-BuLi (0.79 mL) was added,
and the bright yellow suspension was warmed to room tem-
perature. After 20 min, the mixture was diluted with Et2O,
worked up, and concentrated to a clear yellow liquid (0.75 g).
Column chromatography (silica gel; ethyl acetate 0-10%)
yielded (E)-62 (160 mg, 28%), the first eluent, a white crystal-
line solid, mp 60-63 °C: 1H NMR (CDCl3, E-isomer) δ -0.11
(s, 9 H), 1.02 (Ha, dd, J ) 6.5, 4.2 Hz, 2 H), 1.40 (d, J ) 7.1
Hz. 2 H), 1.69 (dd, J ) 6.6, 4.2 Hz, 2 H), 5.5-5.6 (m, 2 H),
7.4-7.8 (m, 5 H); 13C NMR (CDCl3) δ -2.0 (q), 12.8 (t), 23.1
(t), 44.0 (s), 120.6 (d), 128.6 (d), 128.7 (d), 133.0 (d), 135.9 (d),
139.0 (s); mass spectrum m/e calcd for C15H22O2SSi (M+)
(E)- a n d (Z)-4-Ben zyl-5-p h en yl-4-(p h en ylsu lfon yl)-1-
(tr im eth ylsilyl)-2-p en ten es (49). Procedure E, yield 71%,
white crystals: mp 100-101 °C (from hexane): 1H NMR (CCl4,

4192 J . Org. Chem., Vol. 63, No. 13, 1998
Meagher et al.
294.1110, found 294.1108. Anal. Calcd for C15H22O2SSi: C,
61.18; H, 7.53. Found: C, 61.19; H, 7.50.
Allylen ecyclop r op a n e (72, n ) 2). Procedure D gave 83
(n ) 2, 90%) and hexamethyldisiloxane (HMDS) as a colorless
oil stable at room temperature for several days. Diene 72 (n
) 2) turned cloudy upon standing: 1H NMR (CCl4) δ 0.00 (s,
HMDS), 1.05 (s, 4 H), 5.00-5.45 (m, 2 H), 6.32-6.88 (m, 2 H).
The IR and 1H NMR spectra of 72 (n ) 2) are identical with
the literature.15c
The second eluent, (E,Z)-67 (50 mg, 8%), was a clear oil:
1H NMR (CDCl3, E-isomer) δ 0.02 (s, 9 H), 1.57 (d, J ) 8.2
Hz, 2 H), 1.76 (d, J ) 12.7 Hz, 2 H, Ha), 2.27 (ddd, J ) 12.7,
13.0, 4.7 Hz, 2 H, Hb), 3.42 (ddd, J ) 12.5, 11.8, 1.3 Hz, 2 H,
Hc), 3.85 (dd, J ) 11.2, 4.1 Hz, 2 H, Hd), 5.02 (d, J ) 15.9 Hz,
1 H, He), 5.60 (dt, J ) 16.2, 8.0 Hz, 1 H, Hf), 7.4-7.9 (m, 5 H);
13C NMR (CDCl3, E-isomer) δ -1.7, 24.2, 29.4, 63.5, 66.0, 121.7,
128.4, 130.8, 133.5, 135.2, 137.5; NOE differences with ir-
radiation at δ 3.42 gave enhancements at δ 1.76 (3.21%), δ
3.85 (29.63%), δ 5.02 (2.26%), and δ 5.60 (2.46%); NOE
differences with irradiation at δ 3.42 resulted in enhancements
at δ 1.76 (3.21%), δ 3.85 (29.63%), δ 5.02 (2.26%), δ 5.60
(2.46%), and δ 3.42 (25.74%); NOE differences with irradiation
at δ 5.02 led to enhancements at δ 1.57 (5.17%), δ 1.76 (4.76%),
δ 3.42 (2.24%), and δ 7.80 (1.97%); mass spectrum, m/e calcd
for C11H21OSi (M+ - O2SPh) 197.1362, found 197.1371; GC-
CI-MS (CH4) m/e (relative intensity) 339 (100, M+ + 1), 323
(46), 251 (17), 215 (39), 125 (24), 123 (10), 111 (25), 107 (47),
95 (15).
P r oced u r e F for Cycloa lk yla tion of 1-(P h en ylsu lfo-
n yl)-4-(tr im eth ylsilyl)-2-bu ten es (7 a n d 8); (E)- a n d (Z)-
1-(P h en ylsu lfon yl)-1-(3-(t r im et h ylsilyl)-1-p r op en yl)cy-
clop r op a n es (62). n-BuLi (1.60 mL, 3.87 mmol, 2.42 M in
hexane) was added to 7 and 8 (0.96 g, 3.57 mmol) at -78 °C
in THF (10 mL). After 10 min, 1,2-dibromoethane (68, 812
mg, 4.32 mmol) was added. After 1 h, the solution was
recooled to -78 °C and additional n-BuLi (2.20 mL, 5.32 mmol)
was added. The mixture, after warming to room temperature,
was stirred for 1 h, diluted with Et2O, worked up, and
concentrated to a yellow liquid oil (1.23 g). Column chroma-
tography (silica gel; ethyl acetate 0-5%) yielded (E,Z)-62 (1.01
g, 95%), a viscous oil which solidified upon standing; mp 63-
65 °C (from pentane). The product was identical with that
prepared from 15 and 16 with 58 and subsequent ring closure
of 61 (eq 8).
N-P h en yl-4,5-d ia za sp ir o[2.5]oct-7-en e-4,5-d ica r boxim -
id e (73). TBAF (7.13 mL, 7.13 mmol, 1.0 M solution in THF)
was added to 83 (n ) 2; 1.40 g, 4.75 mmol) in THF (15 mL) at
0 °C. After 5 min, the mixture was diluted with Et2O, worked
up, and cooled (-78 °C). 4-Phenyl-1,2,4-triazoline-3,5-dione15g
(0.83 g, 4.75 mmol) was then added in 1 h. The temperature
of the reaction mixture was not allowed to rise above 60 °C.
The mixture was filtered, concentrated to a brown solid (1.10
g), and chromatographed (silica gel; ethyl acetate 25%) to give
73 (0.98 g, 81%) as a white crystalline solid: mp 130-131 °C
(from hexane): 1H NMR (CDCl3) δ -0.92 (dd, J ) 7.6 Hz, 2
H), 2.10 (dd, J ) 7.6 Hz, 2 H), 4.17 (dd, J ) 3.2 Hz, 2 H), 5.22
(dt, J ) 11.2 Hz, 1 H), 5.82 (dt, J ) 11.3 Hz, 1 H), 7.2-7.7 (m,
5 H); 13C NMR (CDCl3) δ 12.0 (t), 40.9 (s), 43.8 (t), 118.3 (d),
125.6 (d), 128.1 (d), 129.1 (d), 130.5 (d), 150.7 (s), 152.4 (s);
mass spectrum, m/e calcd for C14H13N3O2 (M+) 255.1007, found
255.1004. Anal. Calcd for C14H13N3O2: C, 65.87; H, 5.13.
Found: C, 65.47; H, 4.99.
Allylen ecyclobu ta n e (72, n ) 3). Procedure E, yield 61%;
HMDS 22%: 1H NMR (CDCl3) δ 0.08 (s, HMDS), 2.01 (quin,
J ) 7.9 Hz, 2 H), 2.7-2.8 (m, 4 H), 4.91 (Ha, dd, J ) 10.2, 0.9
Hz, 1 H), 4.99 (Hb, dd, J ) 17.0, 0.9 Hz, 1 H), 5.78 (Hc, dt, J )
10.8, 2.2 Hz, 1 H), 6.27 (Hd, ddd, J ) 7.0, 10.8, 10.2 Hz, 1 H);
13C NMR (CDCl3) δ 1.9 (q, HMDS), 17.1 (t), 29.9 (t), 31.3 (t),
113.0 (t), 121.7 (d), 133.1 (d), 146.0 (s); mass spectrum, m/e
calcd for C7H10 (M+) 94.0782, found 94.0789.
Allylen ecyclop en ta n e (72, n ) 4). Procedure C, yield
51%; HMDS 11%: 1H NMR (CDCl3) δ 0.12 (s, HMDS), 1.6-
1.8 (m, 4 H), 2.3-2.4 (m, 4 H), 4.95 (Ha, dd, J ) 9.2, 1.0 Hz, 1
H), 5.04 (Hb, dd, J ) 16.1, 0.8 Hz, 1 H), 5.99 (Hc, d, J ) 10.9,
1 H), 6.46 (Hd, dd, J ) 17.0, 10.6, 10.5 Hz, 1 H); 13C NMR
(CDCl3) δ 1.8 (q, HMDS), 26.1 (t), 26.3 (t), 29.2 (t), 33.8 (t),
113.2 (t), 121.3 (d), 134.7 (d), 147.6 (s); mass spectrum, m/e
calcd for C8H12 (M+) 108.0939, found 108.0955.
(E)- a n d (Z)-1-(P h en ylsu lfon yl)-1-(3-(tr im eth ylsilyl)-1-
p r op en yl)cyclobu ta n es (71, n ) 3). Procedure F, yield 87%,
a colorless oil: 1H NMR (CDCl3, E-isomer) δ -0.06 (s, 9 H),
1.46 (dd, J ) 8.0, 1.0 Hz, 2 H), 1.6-2.3 (m, 4 H), 2.7-3.0 (m,
2 H), 5.29 (d, J ) 15.4 Hz, 1 H), 5.49 (dt, J ) 15.4, 7.9 Hz, 1
H), 7.4-7.9 (m, 5 H); irradiation at δ 1.6-2.3 collapses δ 2.7-
3.0 to a bs; irradiation at δ 1.46 collapses δ 5.49 to a d; 13C
NMR (CDCl3, E-isomer) δ -1.9, 15.1, 23.2, 27.8, 66.9, 123.9,
128.4, 129.6, 133.2, 133.3, 136.3; mass spectrum, m/e calcd for
Allylen ecycloh exa n e (72, n ) 5).15g,h Procedure D, yield
67%: 1H NMR (CDCl3) δ 1.5-1.6 (m, 6 H), 2.15 (bs, 2 H), 2.29
(bs, 2 H), 4.97 (Ha, dd, J ) 10.2, 2.0 Hz, 1 H), 5.10 (Hb, dd, J
) 16.8, 2.0 Hz, 1 H), 5.80 (Hc, d, J ) 10.9 Hz, 1 H), 6.63 (Hd,
ddd, J ) 16.8, 10.8, 10.3 Hz, 1 H); 13C NMR (CDCl3) δ 26.8,
27.7, 28.5, 29.2, 37.2, 114.4, 122.7, 132.7, 144.1; mass spectrum
m/e calcd for C9H14 122.1096, found 122.1094. The spectra of
72 (n ) 5) are identical with that in the literature.15g,h
4-Allylen et et r a h yd r op yr a n (74). Procedure C, yield
87%: 1H NMR (CDCl3) δ 2.27 (t, J ) 5.2 Hz, 2 H), 2.42 (t, J )
5.0 Hz, 2 H), 3.69 (quin, J ) 5.6 Hz, 4 H), 5.02 (Ha, dd, J )
10.2, 1.6 Hz), 5.16 (Hb, dd, J ) 16.8, 1.7 Hz), 5.88 (Hc, d, J )
11.0 Hz), 6.57 (Hd, ddd, J ) 16.7, 10.6, 10.5 Hz); 13C NMR
(CDCl3) δ 30.2, 37.0, 68.5, 69.3, 115.8, 124.3, 131.9, 138.0; GC-
HR-MS, m/e calcd for C8H12O 124.0856, found 124.0872.
C
10H19Si (M+ - O2SC6H5) 167.1256, found 167.1271; CI-MS
(CH4), m/e (relative intensity) 309 (2, M+ + H), 287 (6), 269
(4), 243 (10), 214 (88), 199 (28), 167 (100), 95 (33), 73 (31).
(E)- a n d (Z)-1-(P h en ylsu lfon yl)-1-(3-(tr im eth ylsilyl)-1-
p r op en yl)cyclop en t a n es (71, n ) 4). Procedure F, yield
89%, a liquid: 1H NMR (CDCl3, E- and Z-isomers) δ -0.03 (s,
9 H, Z), 0.08 (s, 9 H, E), 1.43 (dd, J ) 8.00, 0.8 Hz, 2 H), 1.5-
1.8 (m, 6 H), 2.2-2.4 (m, 2 H), 5.03 (dt, J ) 11.6, 1.7 Hz, 2 H,
Z), 5.21 (d, J ) 15.6 Hz, 1 H, E), 5.43 (dt, J ) 15.5, 8.0 Hz, 1
H, E), 5.59 (dt, J ) 11.5, 9.2 Hz, 2 H, Z), 7.4-7.8 (m, 5 H); 13
C
NMR (CDCl3, E-isomer) δ -2.0, 23.3, 23.9, 32.7, 74.4, 125.2,
Ack n ow led gm en t. We thank the National Science
Foundation for support of this research.
128.2, 129.9, 132.8, 133.0, 137.2; mass spectrum, m/e calcd for
C
11H21Si (M+ - O2SPh) 181.1412, found 181.1447.
(E)- a n d (Z)-1-(P h en ylsu lfon yl)-1-(3-(tr im eth ylsilyl)-1-
Su p p or tin g In for m a tion Ava ila ble: Experimental sum-
maries and analytical data for 38e, 38I, 38l, 54, and 55 and
NMR spectra (80 pages). This material is contained in
libraries on microfiche, immediately follows this article in the
microfilm version of the journal, and can be ordered from the
ACS; see any current masthead page for ordering information.
p r op en yl)cycloh exa n es (71, n ) 5). Procedure F, yield 78%,
a colorless oil: 1H NMR (CDCl3, E-isomer) δ -0.02 (s, 9 H),
1.0-1.9, (m, 12 H), 4.92 (dd, J ) 15.9, 1.1 Hz, 1 H), 5.49 (dt,
J ) 15.9, 8.2 Hz, 1 H), 7.4-7.8 (m, 5 H); 13C NMR (CDCl3,
E-isomer) δ -1.9, 21.5, 23.8, 25.1, 28.8, 68.4, 122.9, 128.0,
130.7, 133.0, 135.6, 136.0; mass spectrum, m/e calcd for C12H23
-
Si (M+-O2SPh) 195.1569, found 195.1557.
J O970545K