Highly diastereoselective synthesis of vinylcyclopropane derivatives with (-)-8-phenylmenthol as chiral auxiliary

Article abstract of DOI:10.1021/jo010121x

The silylated telluronium allylide 4, generated in situ from the corresponding telluronium salt in the presence of LiTMP, reacted with (-)-8-phenylmenthyl α,β-unsaturated esters to afford trans-2-silylvinyl-trans-3-substituted cyclopropyl esters with high diastereoselectivity in high yields. The absolute configuration was determined by chemical transformation. A mechanistic rationale is proposed.

Full text of DOI:10.1021/jo010121x

J . Org. Chem. 2001, 66, 5717-5722
5717
High ly Dia ster eoselective Syn th esis of Vin ylcyclop r op a n e
Der iva tives w ith (-)-8-P h en ylm en th ol a s Ch ir a l Au xilia r y
Song Ye, Yong Tang,* and Li-Xin Dai
Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, China
tangy@pub.sioc.ac.cn
Received J anuary 30, 2001
The silylated telluronium allylide 4, generated in situ from the corresponding telluronium salt in
the presence of LiTMP, reacted with (-)-8-phenylmenthyl R,â-unsaturated esters to afford trans-
2-silylvinyl-trans-3-substituted cyclopropyl esters with high diastereoselectivity in high yields. The
absolute configuration was determined by chemical transformation. A mechanistic rationale is
proposed.
In tr od u ction
found that chiral chloroallylphosphonic amide such as
compound 1 could run a formal [2 + 1] cycloaddition
reaction to afford highly functionalized cyclopropane
derivatives in high yield with excellent diastereoselec-
tivity (eq 1). In our previous publications, we have
The vinylcyclopropane derivatives are very useful
intermediates in organic synthesis and ubiquitous sub-
structures of several biologically active compounds,1
notably agrochemicals such as pyrethroids.2 Conse-
quently, development of new methods for the construction
of vinylcyclopropanes continues.3 In view of the difficulty
that can be associated with both the regioselective
introduction of vinyl group and the stereoselective forma-
tion of multisubstituted cyclopropane, most frequently,
many synthetic approaches rely on indirect routes.4 In
particular, for the preparation of optically active vinyl-
cyclopropanes, resolution is still the best method and few
direct asymmetric syntheses of vinylcyclopropanes were
reported in the literatures.5 One of the most successful
examples was discovered by Hanessian’s group.6 They
described that the telluronium allylides could react with
R,â-unsaturated esters or ketones to provide the vinyl-
cyclopropane derivatives in high yields with high stereo-
selectivity.7 We also found that the stereoselectivity of
the reaction of telluronium allylides with R,â-unsaturated
esters or amides could be controlled by the choice of the
base used for the formation of ylide or by the use of
HMPA (Scheme 1). And thus, either of the two geo-
metrical isomers of a polyfunctionalized 3-vinylcyclopro-
pane could be obtained at will with high stereoselectiv-
ity.8 In our continuing studies on the application of ylides
in organic synthesis, we focused on asymmetric synthesis
of vinylcyclopropane derivatives. In this paper, we wish
to report a chiral auxiliary-controlled access to the
optically active trimethylsilylvinylcyclopropane deriva-
tives via ylide routes.
(1) Trost, B. M.; Toste, F. D.; Shen, H. J . Am. Chem. Soc. 2000, 122,
2379. (b) Wender, P. A.; Zhang, L. Org. Lett. 2000, 2, 2323. (c) Wender,
P. A.; Dyckman, A. J .; Husfeld, C. O.; Scanio, M. J . C. Org. Lett. 2000,
2, 1609. (d) Armesto, D.; Ramos, A.; Mayoral, E. P.; Ortiz, M. J .;
Agarrabeitia, A. R. Org. Lett. 2000, 2, 183. (e) Lloyd-J ones, Guy C.;
Murray, M.; Stentiford, R. A.; Worthington, P. A. Eur. J . Org. Chem.
2000, 975. (f) Armesto, D.; Ortiz, M. J .; Agarrabeitia, A. R. J . Org.
Chem. 1999, 64, 1056. (g) Hudlicky, T.; Reed, J . W. Rearrangements
of Vinylcyclopropanes and Related Systems in Comprehensive Organic
Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford,
UK, 1991, vol. 5, pp 899-970. (h) Piers, E. Rearrangements of
Divinycyclopropanes in Comprehensive Organic Synthesis; Trost, B.
M., Fleiming, I., Eds. Pergamon Press: 1991, vol. 5, pp 971-997. (i)
Wang, H. N. C.; Hon, M.-Y.; Tse, C.-W.; Yip, Y.-C.; Tanko, J .; Hudlicky,
T. Chem. Rev. 1989, 89, 165.
(2) Henrick, C. A. Pyrethroids In Agrochemicals from natural
Products; Godfrey, C. R. A., Ed.; Marcel Dekker: New York, 1995; pp
147-213.
(3) Barluenga, J .; Lo´pez, S.; Trabanco, A. A.; Ferna´ndez-Acebes, A.;
Flo´rez, J . J . Am. Chem. Soc. 2000, 122, 8145. (b) Cheng, D.; Knox, K.
R.; Cohen, T. J . Am. Chem. Soc. 2000,122, 412. (c) Bertus, P.; Gandon,
V.; Szymoniak, J . Chem. Commun. 2000, 171. (d) Davies, H. M. L.;
Panaro, S. A. Tetrahedron 2000, 56, 4871. (e) Dorizona, P.; Su, G.;
Ludvig, G.; Nikitina, L.; Paugam, R.; Ollivier, J .; Salau¨, J . J . Org.
Chem. 1999, 64, 4712.
Resu lts a n d Discu ssion
First, we synthesized menthyl cinnamate 6a from (-)-
menthol and cinnamic acid according to literature.9 It
could react with the silylated telluronium allylide 5,
generated in situ from the corresponding telluronium salt
4 in the presence of LiTMP, to form the cyclopropanation
(4) Ba¨ckvall, J . E.; Vågberg, J . O.; Zercher, C.; Geneˆt, J . P.; Denis,
A. J . Org. Chem. 1987, 52, 5430. (b) Yan, T.-H.; Paquette, L. A.
Tetrahedron Lett. 1982, 23, 3227. (c) Krief, A.; Dumont, W.; Pasau,
P.; Lecomte, P. Tetrahedron 1989, 45, 3039. (d) Salauu, J .; Karkour,
B.; Ollivier, J . Tetrahedron 1989, 45, 3151. (e) Trost, B. M. Top. Curr.
Chem. 1986, 133, 3. (f) Piers, E.; J ean, M.; Marrs, P. S. Tetrahedron
Lett. 1987, 28, 5075.
(5) Salau¨n, J . Chem. Rev. 1989, 89, 1247. (b) Martin, S. F.; Hom, R.
K.; Dwyer, M. P. Tetrahedron Lett. 1999, 40, 6721.
(6) Hanessian, S.; Andreotti, D.; Gomtsyan, A. J . Am. Chem. Soc.
1995, 117, 10393.
(7) Huang, Y.-Z.; Tang, Y.; Zhou, Z- L.; Huang, J .-L. J . Chem. Soc.,
Chem. Commun. 1993, 7. (b) Huang;Y.-Z., Tang, Y.; Zhou, Z.-L.; Xia,
W.; Shi, L.-P., J . Chem. Soc., Perkin, Trans. 1 1994, 893. (c) Tang, Y.;
Huang, Y.-Z.; Dai, L.-X.; Chi, Z.-F.; Shi, L.-P. J . Org. Chem. 1997, 62,
954. (d) Tang, Y.; Chi, Z.-F.; Huang, Y.-Z.; Dai, L.-X.; Yu, Y.-H.,
Tetrahedron 1996, 52, 8747. (e) Huang, Y.-Z.; Tang, Y.; Zhou, Z.-L
Tetrahedron, 1997, 53, 1668.
(8) Tang, Y.; Huang, Y.-Z.; Dai, L.-X.; Sun, J .; Xia, W. J . Org. Chem.
1996, 61, 5762. (b) Ye, S.; Yuan, L.; Huang, Z.-Z., Tang, Y.; Dai, L. X.
J . Org. Chem. 2000, 65, 6257.
(9) Lo¨her, H. J .; Oppolzer, W. Helv. Chim. Acta 1981, 64, 2808.
10.1021/jo010121x CCC: $20.00 © 2001 American Chemical Society
Published on Web 07/20/2001

5718 J . Org. Chem., Vol. 66, No. 17, 2001
Ye et al.
Sch em e 1
Sch em e 2
products 7a and 8a smoothly. Though the geometrical
selectivity (cis/trans) is exclusive, the diastereoselectivity
is very low and the de is only 16%.10 Much higher
stereodirecting efficiency of (-)-8-phenylmenthyl, com-
pared to (-)-menthyl, was reported in the conjugated
addition of nucleophilic reagent to R,â-unsaturated es-
ters.11 Thus, we chose (-)-8-phenylmenthol as the aux-
iliary to continue our study and hoped that the phenyl
group could act as a powerful stereodirecting steric
barrier to enhance the diastereoselectivity. As expected,
the reaction of ylide 5 with 8-phenylmenthyl cinnamate
worked well with high selectivity in good yield. The ratio
of the two isomers 7b:8b is up to 92:8.12 Attempts to use
more bulky 8-(2-naphthyl)menthyl instead of (-)-8-
phenylmenthyl led to the same diastereodifferentiation
in this reaction (Scheme 2).
Further studies showed that THF is the best solvent
for this reaction, compared to n-hexane, ether and toluene
(entries 1, 5, 6, and 7 in Table 1). Although LDA and
KHMDS could be used as the base to produce ylide, the
best one is LiTMP as shown in Table 1 (entries 1, 8, and
9). Lowering the reaction temperature just enhanced the
diastereoselectivity a little but low yield was obtained
(entries 2 and 3 in Table 1).
Ta ble 1. Effects of Solven t, Ba se, a n d Tem p er a tu r e on
th e Cyclop r op a n a tion of 8-P h en ylm en th yl Cin n a m a te 6b
w ith Tellu r on iu m Allylid e 5a
entry
6b:4:base
solvent
base
yield (%)b
7b:8bc
1
1:3:3
1:2:2
1:2:2
1:3:3
1:3:3
1:3:3
1:3:3
1:3:3
1:3:3
THF
THF
THF
THF
hexane
ether
toluene
THF
LiTMP
LiTMP
LiTMP
LiTMP
LiTMP
LiTMP
LiTMP
LDA
83
43
32
59
92:8
91:9
93:7
90:10
/
/
/
2d
3d,e
4d
5
tracef
tracef
tracef
6
7
8
9
70
91:9
/
g
THF
KHMDS
a
All reactions were carried out as follows unless otherwise
noted: A mixture of telluronium salt 4 and base in solvent was
stirred at -78 °C for 5-10 min, then R,â-unsaturated ester 6b
was added. The resulting solution was stirred for 2 h at this
temperature and then filtered rapidly through a glass funnel with
a thin layer of silica gel and washed with ethyl acetate. The
combined filtrate was concentrated, and the residue was purified
b
c
by flash chromatography. Isolated yield. The ratio of 7b:8b was
determined by 1H NMR. dThe mixture of telluronium salt 4 and
base was stirred for over 30 min before ester 6b was added. The
e
f
reaction was carried out at -100 °C. Most of the ester 6b could
be recovered. gThe reaction was complicated, and small amount
of 2-cis-trimethylsilylvinyl-3-trans-phenylcycloproapanecarboxylic
ester was isolated.
The good diastereoselectivities obtained with cin-
namate encouraged us to further explore the cyclopro-
panation of other R,â-unsaturated esters. As shown in
Table 2, a variety of R,â-unsaturated esters could react
with silylated allylic telluronium ylide to provide silylvi-
nylcyclopropane derivatives with high diastereoselectiv-
Ta ble 2. Asym m etr ic Cyclop r op a n a tion of Tellu r on iu m
Sa lt 4 w ith r,â-Un sa tu r a ted Ester s
(10) The de value of 7a /8a was determined by HPLC. The relative
stereochemistries of compounds 7a and 8a were determined by
chemical transformatiom as follows. Compound 18, prepared as
reported,8b was hydrolyzed and followed by esterification with (-)-
menthol to afford 7a ′/8a ′ (dr ) 48/52, determined by HPLC) which
have the same 1H NMR spectrum as that of compounds 7a and 8a .
Thus, the relative stereochemistries of compounds 7a and 8a were
assigned as described in Scheme 2.
entry
6
R
yield (%)a
7:8b
1
2
3
4
5
6
7
6b
6d
6e
6f
6g
6h
6i
Ph
H
p-ClC6H4
83
72
94
100
89
94
92:8
86:14
88:12
90:10
89:11
88:12
86:14
p-FC6H4
p-CH3C6H4
p-CF3C6H4
p-CH3OC6H4
90
a
Isolated yields. bThe ratios of compound
7 and 8 were
determined by 1H NMR.
(11) Corey, E. J .; Ensley, H. E. J . Am. Chem. Soc. 1975, 97, 6908.
(b) d’Angelo, J .; Maddaluno, J . J . Am. Chem. Soc. 1986, 108, 8112. (c)
Sato, M.; Aoyagi, S.; Yago, S.; Kibayash, C. Tetrahedron Lett. 1996,
37, 9063.
ity in high yields. It is worth noting that the highly
optically active product could be obtained by recrystal-
lization. For example, compound 7b/8b (84% de) was
recrystallized to afford compound 7b′/8b′ with 95% de
in 57% yield.
(12) The dr value of 7b/8b was determined by 1H NMR. The relative
stereochemistries (cis/trans) were determined by similar chemical
transformation as described in ref 10.

Synthesis of Vinylcyclopropane Derivatives
J . Org. Chem., Vol. 66, No. 17, 2001 5719
Sch em e 3
Sch em e 6
Sch em e 7
Sch em e 4
It is worth to note that the chiral auxiliary (-)-8-
phenylmenthol can be easily recovered in 92% yield by
saponification (Scheme 6). Additionally, the cyclopropane
derivatives prepared by the current method should be
synthetically useful, because these compounds can un-
dergo many chemical transformations. For example,
compound 16 reacted with acetyl chloride to form the
corresponding R,â-unsaturated ketone 17 without loss of
ee (Scheme 7).
Sch em e 5
In conclusion, the synthesis of optically active vinyl-
cyclopropane derivatives was developed by using (-)-8-
phenylmenthol as the chiral auxiliary. The easy recovery
of chiral auxiliary, good selectivity, and high yield make
it a potentially useful method in organic synthesis. The
reagent-controlled and catalytically asymmetric synthesis
of vinylcyclopropane derivatives is in progress in our
laboratory.
The absolute configurations of the products 7b and 7d
were determined by chemical transformations. By treat-
ment of compound 7b/8b with concentrated sulfuric acid,
the desilylated compound 9 was formed. Saponification
of compound 9, followed by esterification with tert-butyl
alcohol, provided tert-butyl ester 11. After one-pot ozo-
nization and reduction of compound 11, the known
Exp er im en ta l Section
All reaction flasks were dried by flame, and all reactions
were carried out under argon. THF was dried by distillation
over sodium-benzophenone ketyl. The reagents were pur-
chased from commercial sources and used directly.
compound 12 6 ([R]20 ) -92.1°, c ) 1.23, CHCl3) was
D
obtained. By comparison of the rotation, the configuration
of compound 12 was assigned to be 1S,2S,3R. Thus the
configuration of compound 7b was assigned to be 1R,2S,3R
(Scheme 3). Cyclopropanation product 7d was desilylated
and then hydrolyzed to form 2-vinylcyclopropanecarboxy-
Gen er a l P r oced u r e for P r ep a r a tion of th e r,â-Un sa t-
u r a ted Ester s.9 To a solution of (-)-menthol (4.69 g, 30
mmol), cinnamic acid (4.89 g, 33 mmol), and DMAP (138 mg,
1.5 mmol) in dichloromethane (40 mL) at 0 °C was added DCC
(7.43 g, 36 mmol) in dichloromethane (20 mL). Then, the
reaction mixture was allowed to warm to room temperature.
After being stirred for 10 h, the reaction mixture was passed
through a short silica gel column, which was eluted with ethyl
acetate. Upon removal of the solvent under vacuum, the
residue was purified by column chromatrography.
lic acid 14 which has the same rotational direction ([R]20
D
) +107°, c ) 0.7, EtOH) as the known enantiomer13
([R]20 ) +165°, c ) 2.1, EtOH) (Scheme 4). Thus, the
D
absolute configuration of compound 7d is 1S,2R.
It was well-known that there always has the π-stacking
effect between the phenyl and dienyl group in (-)-8-
phenylmenthyl esters of R,â-unsaturated acid.14 As shown
in Scheme 5, the phenyl group was proposed to block the
Si face of the carbon-carbon double bond. The telluro-
nium ylide attacked at C-3 on Re face, so compound 7b
was sterically preferred and formed as the major product.
Men th yl Cin n a m a te (6a ).15 Yield: 63%. 1H NMR (300
MHz, CDCl3, TMS) δ 7.67 (d, J ) 15.9 Hz, 1H), 7.50 (m, 2H),
7.40 (m, 3H), 6.43 (d, J ) 15.8 Hz, 1H), 4.83 (dt, J ) 4.4, 10.9
Hz, 1H), 0.7-2.2 (m, 9H), 0.93 (d, J ) 2.2 Hz, 3H), 0.91 (d, J
) 2.8 Hz, 3H), 0.79 (d, J ) 7.0 Hz, 3H).
8-P h en ylm en th yl Cin n a m a te (6b).16 Yield: 55%. [R]20
D
1
) +9.9° (c 2.23, CHCl3); H NMR (300 MHz, CDCl3, TMS) δ
7.5-7.1 (m, 11H), 5.75 (d, J ) 16.0 Hz, 1H), 4.91 (dt, J ) 4.4,
(13) Fritschi, H.; Leutenegger, U.; Pfalta, A. Helv. Chim. Acta 1988,
71, 1553.
(14) Dumas, F.; Mezrhab, B.; d′Angelo, J . J . Org. Chem. 1996, 61,
2293. (b) J ones, G. B.; Chapman, B. J . Synthesis 1995, 475. (c) Kojima,
S.; Fujitomo, K.; Shinohara, Y.; Shimizu, M.; Ohkata, K Tetrahedron
Lett. 2000, 41, 9847.
(15) Meth-Cohn, O. Organic Syntheses; Wiley: New York, 1993;
Collect. Vol. VIII, p 350.
(16) Fleming, I.; Kindon, N. D. J . Chem. Soc., Perkin Trans. 1 1995,
303.

5720 J . Org. Chem., Vol. 66, No. 17, 2001
Ye et al.
10.7 Hz, 1H), 2.11 (dt, J ) 3.4, 12.1 Hz, 1H), 2.0-0.9 (m, 7H),
1.32 (s, 3H), 1.23 (s, 3H), 0.88 (d, J ) 6.5 Hz, 3H).
mmol, made from 2,2,6,6-tetramethylpiperidine and n-butyl-
lithium in situ) at -78 °C. After stirring for 3-5 min, the R,â-
unsaturated ester 6 (0.418 mmol) in THF (1 mL) was added.
The resulting solution was stirring for 4 h at -78 °C, and then
several drops of water were added to quench the reactions.
The reaction mixture was passed through a short silica gel
column, which was eluted with ethyl acetate. After concentra-
tion of the elution, the residue was purified by preparative
thin-layer chromatography.
Cyclop r op a n e Der iva tive 7a . Yield: 89%. 7a /8a ) 58/
42;10 IR (film) ν/cm-1 3063 (w), 2957 (s), 1722 (vs), 1613 (m),
1174 (s); 1H NMR for 7a and 8a (300 MHz, CDCl3, TMS) δ
7.6-7.4 (m, 5H), 6.15 (d, J ) 18.6 Hz, 1H), 5.59 (dd, J ) 8.7,
18.6 Hz, 1H), 5.01 (dt, J ) 6.8, 10.8 Hz, 1H), 3.25-3.15 (m,
1H), 2.75-2.65 (m, 1H), 2.50 (t, J ) 4.7 Hz, 1H), 2.5-1.0 (m,
9H), 1.20 (d, J ) 3.2 Hz, 3H), 1.18 (d, J ) 3.1 Hz, 3H), 1.06 (d,
J ) 7.0 Hz, 3H), 0.18 (s, 9H); MS (EI, m/ z, rel intensity) 399
(M+, 0.39), 383 (5.0), 261 (22.5), 139 (35), 83 (100). Anal. Calcd
for C25H38O2Si: C, 75.33; H, 9.61. Found: C, 74.93; H, 9.52.
8-(2-Na p h th yl)m en th yl Cin n a m a te (6c). Yield: 26%
(recovered 8-(2-naphthyl)menthol, 31%). IR (KBr) ν/cm-1 3078
1
(w), 2953 (s), 1703 (vs), 1637 (s), 1310 (s), 1176 (vs); H NMR
(300 MHz, CDCl3, TMS) δ 7.5-7.1 (m, 10H), 7.02 (d, J ) 16
Hz, 1H), 6.88 (d, J ) 7.1 Hz, 2H), 5.25 (d, J ) 16.0 Hz, 1H),
4.95 (dt, J ) 4.3, 10.7 Hz, 1H), 2.26 (dt, J ) 3.5, 12.0 Hz, 1H),
2.0-0.9 (m, 7H), 1,44 (s, 3H), 1.30 (s, 3H), 0.89 (d, J ) 6.5 Hz,
3H); MS (EI, m/ z, rel intensity) 412 (M+, 14.4), 169 (100), 141
(19), 77 (13). Anal. Calcd for C29H32O2: C, 84.43; H, 7.82.
Found: C, 84.13; H, 7.85.
1
Ester 6d .17 Yield: 46%. H NMR (300 MHz, CDCl3, TMS)
δ 7.30-7.21 (m, 4H), 7.05-7.03 (m, 1H), 5.98-5.90 (m, 1H),
5.55-5.47 (m, 2H), 4.79 (dt, J ) 4.2, 10.7 Hz, 1H), 2.0-1.93
(m, 1H), 1.86-1.74 (m, 1H), 1.63-1.53 (m, 2H), 1.43-1.35 (m,
1H), 1,23 (s, 3H), 1.15 (s, 3H), 0.79 (d, J ) 6.6 Hz, 3H), 1.2-
0.6 (m, 3H).
Ester 6e. Yield: 52%. mp 69-71 °C; [R]20D ) +23.9° (c 1.03,
CHCl3); IR (KBr) ν/cm-1 3085 (w), 2952 (s), 1706 (vs), 1640
(s), 1492 (s), 1310 (s), 1187 (s); 1H NMR (300 MHz, CDCl3,
TMS) δ 7.5-7.0 (m, 10H), 5.68 (d, J ) 16 Hz, 1H), 4.91 (dt,
4.4, 10.7 Hz, 1H), 2.2-0.8 (m, 8H), 1,32 (s, 3H), 1.22 (s, 3H),
0.89 (d, J ) 6.5 Hz, 3H); MS (EI, m/ z, rel intensity) 397 (M+,
Cyclop r op a n e Der iva tive 7b. Yield: 83%. 7b/8b ) 92:
8;12 IR (film) ν/cm-1 3089 (w), 2955 (s), 1718 (vs), 1611 (m),
1
1248 (s), 1174 (s), 860 (s). H NMR (300 MHz, CDCl3, TMS) δ
7.4-7.1(m, 10H), 5.89 (d, J ) 18.6 Hz, 1H), 5.34 (dd, J ) 8.7,
18.5 Hz, 1H), 4.95 (dt, J ) 4.4, 10.8 Hz, 1H), 2.92 (dd, J ) 9.7,
5.3 Hz, 0.92H, 7b-PhCH), 2.65 (dd, J ) 9.8, 5.5 Hz, 0.08H,
8b-PhCH), 2.36 (dt, J ) 8.9, 4.5 Hz, 1H), 1.89 (dd, J ) 5.1, 4.8
Hz, 1H), 2.2-0.9 (m, 8H), 1.46 (s, 3H), 1.35 (s, 3H), 0.99 (d, J
) 6.8 Hz, 3H), 0.01 (s, 9H); 13C NMR (75 MHz, CDCl3 TMS) δ
172.0, 151.2, 142.0, 136.0, 132.9, 129.0, 128.0, 127.9, 126.5,
125.3, 125.2, 75.1, 50.6, 41.9, 39.8, 34.6, 34.0, 32.0, 31.3, 27.4,
27.1, 26.8, 26.3, 21.8, -1.4; MS (EI, m/ z, rel intensity) 460
(M+ - 15, 0.35), 215 (3.93), 119 (52), 105 (100), 91 (26). Anal.
Calcd for C31H42O2Si: C, 78.43; H, 8.92. Found: C, 78.08; H,
8.53.
0.2), 215 (34.1), 119 (100), 91 (33). Anal. Calcd for C25H29
-
ClO2: C, 75.64; H, 7.36; Cl, 8.93. Found: C, 75.53; H, 7.31;
Cl, 8.87.
Ester 6f. Yield: 63.5%. mp 76-78 °C; [R]20D ) +7.3° (c 1.07,
CHCl3); IR (KBr) ν/cm-1 3085 (w), 2953 (s), 1706 (vs), 1641
1
(s), 1602 (s), 1510 (s), 1313 (s), 1179 (vs). H NMR (300 MHz,
CDCl3, TMS) δ 7.5-7.0 (m, 10H), 5.65 (d, J ) 16.0 Hz, 1H),
4.91 (dt, J ) 4.33, 10.7 Hz, 1H), 2.12 (dt, J ) 3.46, 12.0 Hz,
1H), 2.0-1.90 (m, 1H), 1.85-1.75 (m, 1H), 1.75-1.65 (m, 1H),
1.60-1.45 (m, 1H), 1.32 (s, 3H), 1.22 (s, 3H), 0.88 (d, J ) 6.5
Hz, 3H), 1.3-0.8 (m, 3H); MS (EI, m/ z, rel intensity) 381 (M+,
0.46), 215 (53), 119 (100), 105 (42), 91 (26). Anal. Calcd for
Cyclop r op a n e Der iva tive 7c. Yield: 94%. 7c/8c ) 90:10;
IR (KBr) ν/cm-1 3057 (w), 2955 (s), 1713 (vs), 1630 (m), 1175
(s); 1H NMR (300 MHz, CDCl3, TMS) δ 8.0-7.8 (m, 12H), 5.92
(d, J ) 18.5 Hz, 0.10H, 8c-TMSCHd), 5.80 (d, J ) 18.6 Hz,
0.90H, 7c-TMSCHd), 5.25 (dd, J ) 18.6, 8.7 Hz, 1H), 5.05 (dt,
J ) 4.3, 10.7 Hz, 1H), 2.93 (dd, J ) 9.6, 5.4 Hz, 0.90H, 7c-
PhCH), 2.60 (dd, J ) 9.6, 5.4 Hz, 0.10H, 8c-PhCH), 2.4-1.0
(m, 10H), 1,62 (s, 3H), 1.48 (s, 3H), 1.00 (d, J ) 6.4 Hz, 3H),
0.00 (s, 9H); 13C NMR (75 MHz, CDCl3 TMS) δ 172.1, 148.8,
142.0, 135.9, 133.4, 132.7, 131.5, 129.0, 128.04, 127.98, 127.5,
127.3, 126.4, 125.8, 125.2, 124.8, 123.3, 75.3, 50.2, 41.9, 40.2,
34.6, 33.9, 31.9, 31.4, 27.3, 27.2, 27.0, 26.4, 21.8, -1.4; MS (EI,
m/ z, rel intensity) 526 (M+, 5), 265 (35), 169 (100), 141 (40).
Anal. Calcd for C35H44O2Si: C, 84.10; H, 8.45. Found: C, 80.12;
H, 8.52.
Cyclop r op a n e Der iva tive 7d . Yield: 72%. 7d /8d ) 86:
14; IR (film) ν/cm-1 3060 (w), 2955 (s), 1716 (vs), 1607 (m),
1513(s), 1176 (s); 1H NMR (400 MHz, CDCl3, TMS) δ 7.3-7.1
(m, 4H), 7.1-7.0 (m, 1H), 5.76 (d, J ) 18.5 Hz, 0.14H, 7d-
TMSCHd), 5.68 (d, J ) 18.5 Hz, 0.86H, 8d -TMSCHd), 5.38
(dd, J ) 8.3, 18.5 Hz, 1H), 4.78 (dt, J ) 6.2, 10.6 Hz, 1H),
2.1-1.9 (m, 1H), 1.9-1.75 (m, 2H), 1.7-1.6 (m, 2H), 1.50-
1.32 (m, 2H), 1,27 (s, 3H), 1.21 (s, 3H), 0.84 (d, J ) 6.5 Hz,
3H), 1.3-0.7 (m, 5H), 0.0 (s, 9H); MS (EI, m/ z, rel intensity)
384 (M+ - 15, 0.96), 215 (7.05), 119 (100), 91 (29). Anal. Calcd
for C25H38O2Si: C, 75.32; H, 9.61. Found: C, 75.54; H, 9.88.
Cyclop r op a n e Der iva t ive 7e. Yield: 94%. 7e/8e ) 88:
12; IR (film) ν/cm-1 3090 (w), 2955 (s), 2923 (s), 1716 (vs), 1600
(w), 1495 (s), 1174 (s); 1H NMR (300 MHz, CDCl3, TMS) δ 7.3-
7.2 (m, 6H), 7.2-7.0 (m, 3H), 5,85 (d, J ) 18.5 Hz, 1H), 5.29
(dd, J ) 8.5, 18.5 Hz, 1H), 4.94 (dt, J ) 4.3, 10.8 Hz, 1H), 2.83
(dd, J ) 9.6, 5.3 Hz, 0.88H, 7e-p-ClC6H4CH), 2.56 (dd, J )
9.6, 5.4 Hz, 0.12H, 8e-p-ClC6H4CH), 2.33 (dt, J ) 9.2, 4.6 Hz,
1H), 2.19 (dt, J ) 3.5, 18.1 Hz, 1H), 2.05-1.95 (m, 1H), 1.85-
1.65 (m, 2H), 1.6-1.4 (m, 1H), 1.43 (s, 3H), 1.32 (s, 3H), 0.95
(d, J ) 6.5 Hz, 3H), 1.4-0.9 (m, 4H), 0.0 (s, 9H); 13C NMR (75
MHz, CDCl3 TMS) δ 171.5, 151.2, 141.2, 134.5, 133.4, 132.2,
130.3, 128.0, 127.9, 125.2, 125.0, 75.0, 50.4, 41.7, 40.0, 34.5,
33.8, 31.2, 31.0, 27.5, 27.2, 26.6, 25.6, 21.7, -1.4; MS (EI, m/ z,
rel intensity) 494 (M+ - 15, 0.35), 215 (6.32), 119 (80), 105
C
25H29FO2: C 78.92; H, 7.68. Found: C, 79.38; H, 7.90.
Ester 6g. Yield: 56%. [R]20 ) +23.7° (c 1.34, CHCl3); IR
D
(film) ν/cm-1 3087 (w), 2952 (s), 1705 (vs), 1635 (vs), 1608 (vs),
1309 (vs), 1270 (vs), 1093 (s). 1H NMR (300 MHz, CDCl3, TMS)
δ 7.5-7.0 (m, 10H), 5.72 (d, J ) 16 Hz, 1H), 4.92 (dt, J ) 6.4,
10.7 Hz, 1H), 2.36 (s, 3H), 2.10 (dt, J ) 3.4, 12.1 Hz, 1H), 1.98-
1.91 (m, 1H), 1.80-1.60 (m, 2H), 1.60-1.40 (m, 1H), 1,32 (s,
3H), 1.23 (s, 3H), 1.3-0.8 (m, 3H), 0.87 (d, J ) 6.5 Hz, 3H);
MS (EI, m/ z, rel intensity) 376 (M+, 0.14), 214 (9.66), 162 (22),
119 (100), 91 (48). Anal. Calcd for C26H32O2: C, 82.94; H, 8.56.
Found: C, 83.05; H, 8.58.
Ester 6h . Yield: 67.5%. mp 82-84 °C; [R]20D ) +7.5° (c 1.07,
CHCl3); IR (KBr) ν/cm-1 3085 (w), 2963 (s), 1706 (vs), 1644
1
(s), 1366 (s), 1336 (s), 1282 (s), 1192 (s); H NMR (300 MHz,
CDCl3, TMS) δ 7.64 (d, J ) 8.2 Hz, 2H), 7.47 (d, J ) 8.1 Hz,
2H), 7.4-7.0 (m, 6H), 5.75 (d, J ) 16 Hz, 1H), 4.92 (dt, J )
4.4, 10.7 Hz, 1H), 2.3-2.0 (m, 1H), 2.0-1.8 (m, 2H), 1.8-1.7
(m, 1H), 1.60-1.40 (m, 1H), 1.32 (s, 3H), 1.22 (s, 3H), 1.3-0.8
(m, 3H), 0.89 (d, J ) 6.5 Hz, 3H); MS (EI, m/ z, rel intensity)
411 (M+ - 19, 0.39), 214 (3.14), 199 (12), 119 (100), 105 (3.5),
91 (21). Anal. Calcd for C26H29F3O2: C, 72.54; H, 6.79. Found:
C, 72.67; H, 6.92.
Ester 6i. Yield: 51.6%. mp 88-90 °C; [R]20 ) +33.8° (c
D
1.02, CHCl3); IR (KBr) ν/cm-1 3080 (w), 2953 (m), 1702 (s),
1636 (m), 1604 (s), 1512 (s), 1172 (vs); 1H NMR (300 MHz,
CDCl3, TMS) δ 7.5-7.0 (m, 8H), 6.88 (d, J ) 8.8 Hz, 2H), 5.65
(d, J ) 16 Hz, 1H), 4.90 (dt, J ) 4.3, 10.8 Hz, 1H), 3.84 (s,
3H), 2.0-0.8 (m, 7H), 1.40 (dt, J ) 3.4, 12.1 Hz, 1H), 1.32 (s,
3H), 1.22 (s, 3H), 0.88 (d, J ) 6.5 Hz, 3H); MS (EI, m/ z, rel
intensity) 392 (M+, 14.7), 178 (94), 161 (69), 119 (100), 91 (50).
Anal. Calcd for C26H32O3: C, 79.56; H, 8.22. Found: C, 79.53;
H, 8.28.
Gen er a l P r oced u r e for Cyclop r op a n a tion Rea ction
via Tellu r on iu m Ylid e. To a solution of telluronium salt 4
(544 mg, 1.25 mmol) in THF (2 mL) was added LiTMP (1.25
(17) Drewes, S. E.; Emslie, N. D.; Khan, A. A. Synth. Commun. 1993,
23, 1215.

Synthesis of Vinylcyclopropane Derivatives
J . Org. Chem., Vol. 66, No. 17, 2001 5721
(100), 91 (33). Anal. Calcd for C31H41ClO2Si: C, 73.12; H, 8.05;
Cl, 6.96. Found: C, 73.00; H, 8.43; Cl, 7.12.
concentrated, and water (20 mL) was added. The mixture was
extracted with ether, dried over Na2SO4, and concentrated. The
residue was purified by column chromatography to afford a
colorless oil 570 mg (83%). IR (film) ν/cm-1 3088 (w), 2956 (s),
1716 (vs), 1278 (m), 1189 (s); 1H NMR (300 MHz, CDCl3, TMS)
δ 7.4-7.0 (m, 10H), 5.2-4.9 (m, 3H), 4.85 (dt, J ) 10.7, 4.4
Hz, 1H), 2.82 (dd, J ) 9.7, 5.5 Hz, 1H), 2.23 (dt, J ) 4.9, 3.8
Hz, 1H), 2.1-2.0 (m, 1H), 2.0-1.9 (m, 1H), 1.75 (t, J ) 5.0
Hz, 1H), 1.36 (s, 3H), 1.25 (s, 3H), 0.90 (s, 3H), 1.7-0.9 (m,
6H); MS (EI, m/ z, rel intensity) 283 (M+ - 119, 2.49), 119
(76.63), 105 (100), 91 (33). Anal. Calcd for C28H34O2: C, 83.54;
H, 8.51. Found: C, 83.58; H, 8.48.
Cyclop r op a n e Der iva t ive 7f. Yield: 100%. 7f/8f ) 90:
10; IR (film) ν/cm-1 3056 (w), 2955 (s), 2924 (m), 1717 (vs),
1607 (m), 1513 (s), 1176 (s); 1H NMR (300 MHz, CDCl3, TMS)
δ 7.38 (d, J ) 7.8 Hz, 2H), 7.32-7.26 (m, 2H), 7.17-7.01 (m,
5H), 5,89 (d, J ) 18.6 Hz, 1H), 5.28 (dd, J ) 8.6, 18.6 Hz, 1H),
4.95 (dt, J ) 4.3, 10.7 Hz, 1H), 2.86 (dd, J ) 9.5, 5.3 Hz, 0.90H,
7f-p-FC6H4CH), 2.58 (dd, J ) 9.7, 5.5 Hz, 0.10H, 8f-p-
FC6H4CH), 2.40-2.28 (m, 1H), 2.2-2.1 (m, 1H), 2.04-1.95 (m,
1H), 1.72 (t, J ) 4.9, 1H), 1.75-1.65 (m, 2H), 1,65-1.5 (m,
1H), 1.46 (s, 3H), 1.34 (s, 3H), 0.96 (d, J ) 6.4 Hz, 3H), 1.5-
0.9 (m, 3H), 0.0 (s, 9H); 13C NMR (75 MHz, CDCl3 TMS) δ
P r ep a r a tion of Acid 10. A solution of 9 (535 mg, 1.33
mmol) and potassium hydroxide (1.49 g, 26.6 mmol) in methyl
alcohol (15 mL) was refluxed for 2 h. The resulting mixture
was concentrated, and then water (20 mL) was added. The
residue was acidified with 10% HCl and extracted with ethyl
acetate, and then the combined extraction was dried and
concentrated. The residue was purified by column chromatog-
raphy to give acid 10. Yield: 96%. mp 74-76 °C; [R]20D ) +5.7°
(c ) 0.91, CHCl3); IR (film) ν/cm-1 3000 (s, br), 1695 (vs), 1459
1
171.8, 161.6 (d, J CF ) 244.0 Hz), 151.3, 141.7, 133.3, 131.7
(d, 4J CF ) 3.2 Hz), 130.6 (d, 3J CF ) 7.9 Hz), 128.0, 125.4, 125.1,
114.8 (d, 2J CF ) 21.0 Hz), 75.1, 50.5, 41.9, 39.8, 34.6, 33.8, 31.3,
31.1, 27.5, 27.3, 26.8, 26.1, 21.8, -1.4; MS (EI, m/ z, rel
intensity) 477 (M+ - 15, 0.21), 215 (5.41), 119 (73), 105 (100),
91 (33). Anal. Calcd for C31H41FO2Si: C, 75.56; H, 8.39.
Found: C, 75.52; H, 8.18.
Cyclop r op a n e Der iva tive 7g. Yield: 89%. 7g/8g ) 89:
1
11; IR (film) ν/cm-1 3050 (w), 2954 (s), 2923 (m), 1717 (vs),
(m), 699 (m); H NMR (300 MHz, CDCl3, TMS) δ 7.4-7.1 (m,
1
1610 (m), 1173 (s); H NMR (300 MHz, CDCl3, TMS) δ 7.39-
5H), 5.4-5.0 (m, 3H), 3.01 (dd, J ) 9.6, 5.3 Hz, 1H), 2.52 (dt,
J ) 9.4, 4.5 Hz, 1H), 2.21 (t, J ) 4.9 Hz, 1H); MS (EI, m/ z, rel
intensity) 171 (13.86), 143 (67.07), 135 (62.85), 115 (19.48),
57 (100). Anal. Calcd for C12H12O2: C, 76.58; H, 6.42. Found:
C, 76.50; H, 6.50.
7.26 (m, 4H), 7.18-7.01 (m, 5H), 5.88 (d, J ) 18.6 Hz, 1H),
5.31 (dd, J ) 8.7, 18.6 Hz, 1H), 4.94 (dt, J ) 4.3, 10.7 Hz, 1H),
2.87 (dd, J ) 9.5, 5.4 Hz, 0.89H, 7g-p-CH3C6H4CH), 2.63 (dd,
J ) 9.4, 5.2 Hz, 0.11H, 8g-p-CH3C6H4CH), 2.40 (s, 3H), 2.30-
2.28 (m, 2H), 2.16-2.0 (m, 2H), 1.85 (t, J ) 4.9, 1H), 1.70 (br
d, J ) 11.6, 2H), 1.65-1.5 (m, 1H), 1.45 (s, 3H), 1.34 (s, 3H),
0.95 (d, J ) 6.4 Hz, 3H), 1.5-0.9 (m, 2H), 0.01 (s, 9H); 13C
NMR (75 MHz, CDCl3 TMS) δ 172.0, 151.1, 142.2, 135.9, 132.9,
132.6, 128.9, 128.6, 127.9, 125.3, 125.1, 75.0, 50.5, 41.8, 39.8,
34.6, 34.1, 31.7, 31.3, 27.5, 26.9, 26.8, 26.4, 21.8, 21.0, -1.4;
MS (EI, m/ z, rel intensity) 474 (M+ - 15, 0.13), 216 (3.38),
119 (62), 105 (100), 91 (35). Anal. Calcd for C32H44O2Si: C,
78.63; H, 9.07. Found: C, 78.65; H, 9.15.
P r ep a r a tion of Ester 11. To a solution of tert-butyl alcohol
(170 mg, 2.3 mmol), acid 10 (216 mg, 1.15 mmol), and DMAP
(140 mg, 1.15 mmol) in dichloromethane (8 mL) at 0 °C was
added DCC (474 mg, 2.3 mmol) in dichloromethane (4 mL).
The reaction mixture was allowed to warm to room temper-
ature and was stirred for 10 h. The reaction mixture was
passed through a short silica gel column, which was eluted
with ethyl acetate. Upon removal of the solvent under vacuum,
the residue was purified by column chromatography. Yield:
Cyclop r op a n e Der iva tive 7h . Yield: 94%. 7h /8h ) 88:
72%. [R]20 ) +7.2° (c ) 1.14, CHCl3); IR (film) ν/cm-1 2980
D
12; IR (film) ν/cm-1 3080 (w), 2955 (s), 2925 (s), 1717 (vs), 1618
(m), 2120 (w), 1720 (vs), 1285 (m), 1151 (s); 1H NMR (300 MHz,
CDCl3, TMS) δ 7.4-7.1 (m, 5H), 5.3-4.9 (m, 3H), 2.85 (dd, J
) 9.6, 5.4 Hz, 1H), 2.37 (dt, J ) 8.8, 4.8 Hz, 1H), 2.14 (t, J )
4.9 Hz, 1H), 1.49 (s, 9H); MS (EI, m/ z, rel intensity) 243 (M+
- 1, 1.44), 143 (18.84), 119 (79.93), 105 (100). Anal. Calcd for
1
(s), 1325 (vs), 1166 (s), 1127 (s); H NMR (300 MHz, CDCl3,
TMS) δ 7.64 (d, J ) 8.2 Hz, 2H), 7.5-7.2 (m, 6H), 7.13 (t, J )
8.2 Hz, 1H), 5.89 (d, J ) 18.5 Hz, 1H), 5.31 (dd, J ) 8.3, 18.5
Hz, 1H), 4.99 (dt, J ) 4.3, 10.7 Hz, 1H), 2.92 (dd, J ) 9.7, 5.4
Hz, 0.88H, 7h -p-CF3C6H4CH), 2.61 (dd, J ) 9.9, 5.7 Hz, 0.12H,
8h -p-CF3C6H4CH), 2.4-2.3 (m, 1H), 2.25-2.1 (m, 1H), 2.1-
2.0 (m, 1H), 1.9-1.7 (m, 3H), 1.7-1.5 (m, 1H), 1.45 (s, 3H),
1.33 (s, 3H), 0.98 (d, J ) 6.4 Hz, 3H), 1.5-1.0 (m, 3H), 0.01 (s,
9H); 13C NMR of 7h ′ (recrystallized, de ) 100%), (75 MHz,
CDCl3 TMS) δ 171.6, 151.4, 140.8, 140.4, 134.2, 129.4, 128.8
(q, 2J CF ) 32.0 Hz), 125.4, 125.2, 124.9 (q, 3J CF ) 3.8 Hz), 124.4
C
16H20O2: C, 78.65; H, 8.25. Found: C, 79.13; H, 8.01.
P r ep a r a tion of 12.6 A solution of 11 (137 mg, 0.56 mmol)
in a mixed solvent of methyl alcohol/dichloromethane (1:1, 16
mL) was treated with a stream of O3 in -78 °C until starting
material could not be detected by TLC analysis (about 30 min).
The reaction mixture was flushed with argon to remove
residual O3, and then NaBH4 (25 mg, 0.67 mmol) was added.
The reaction mixture was allowed to warm to room temper-
ature and stirred 6 h. The reaction mixture was passed
through a short silica gel column, which was eluted with ethyl
acetate. Purification by silica gel chromatography provided 94
1
(q, J CF ) 270.0 Hz), 75.3, 50.5, 41.9, 39.8, 34.6, 34.1, 31.5,
31.4, 27.8, 27.3, 26.7, 25.6, 21.8, -1.5; MS (EI, m/ z, rel
intensity) 524 (M+ - 15, 0.12), 215 (7.6), 119 (68), 105 (100),
91 (42). Anal. Calcd for C32H41F3O2Si: C, 70.81; H, 7.61.
Found: C, 71.11; H, 7.70.
mg (67%) of the alcohol. [R]20 ) -92° (c ) 1.23, CHCl3), (ref:6
D
Cyclop r op a n e Der iva tive 7i. Yield: 90%. 7i/8i ) 86:14;
IR (film) ν/cm-1 3090 (w), 2953 (s), 1717 (vs), 1612 (s), 1515
(s), 1248 (s), 1173 (s); 1H NMR (300 MHz, CDCl3, TMS) δ 7.39-
7.28 (m, 4H), 7.2-7.1 (m, 3H), 6.90 (d, J ) 8.6 Hz, 2H), 5.88
(d, J ) 18.6 Hz, 1H), 5.34 (dd, J ) 8.7, 18.5 Hz, 1H), 4.94 (dt,
J ) 4.3, 10.7 Hz, 1H), 3.86 (s, 3H), 2.85 (dd, J ) 9.5, 5.3 Hz,
0.86H, 7i-p-CH3OC6H4CH), 2.60 (dd, J ) 9.4, 5.1 Hz, 0.14H,
8i-p-CH3OC6H4CH), 2.37-2.28 (m, 1H), 2.2-1.95 (m, 2H), 1.8
(t, J ) 4.8 Hz, 1H), 1.7-1.67 (m, 2H), 1.6-1.5 (m, 1H), 1.46
(s, 3H), 1.34 (s, 3H), 1.5-1.0 (m, 3H), 0.95 (d, J ) 6.4 Hz, 3H),
0.00 (s, 9H); 13C NMR (75 MHz, CDCl3 TMS) δ 172.1, 158.2,
151.1, 142.3, 132.6, 130.1, 128.0, 127.9, 125.3, 125.1, 113.4,
76.6, 55.1, 50.5, 41.8, 39.8, 34.6, 34.0, 31.3, 27.6, 26.9, 26.8,
26.5, 21.8, -1.4; MS (EI, m/ z, rel intensity) 474 (M+ - 31,
0.11), 289 (7.3), 246 (14), 119 (68), 105 (100), 91 (42). Anal.
Calcd for C32H44O3Si: C, 76.14; H, 8.78. Found: C, 75.98; H,
8.63.
[R]20D ) +122.1°, c ) 1.23, CHCl3); 1H NMR (300 MHz, CDCl3,
TMS) δ 7.4-7.1 (m, 5H), 3.55 (m, 1H), 3.4 (m, 1H), 2.82 (dd, J
) 8.6, 5.9 Hz, 1H), 2.05 (m, 2H), 1.48 (s, 9H).
Deter m in a tion of th e Absolu te Con figu r a tion of 7d
P r ep a r a tion of Ester 13. A solution of 7d (235 mg, 0.589
mmol) and concentrated sufuric acid (0.07 mL) in methyl
alcohol (15 mL) was refluxed for 23 h. After concentration, to
the residue was added water (10 mL). The resulting mixture
was extracted with ether, dried over Na2SO4, and concentrated.
The residue was purified by column chromatography to give
13. Yield: 67%. IR (film) ν/cm-1 3088 (w), 2956 (s), 1718 (vs),
1
1394(s), 1178 (s), 700 (s); H NMR (300 MHz, CDCl3, TMS) δ
7.30-7.20 (m, 4H), 7.15-7.05 (m, 1H), 5.4-5.2 (m, 1H), 5.1-
5.0 (m, 1H), 5.0-4.9 (m, 1H), 4.78 (dt, J ) 10.7, 4.4 Hz, 1H),
2.1-1.9 (m, 1H), 1.9-0.7 (m, 11H), 1.31 (s, 3H), 1.20 (s, 3H),
0.86 (d, J ) 6.5 Hz, 3H); MS (EI, m/ z, rel intensity) 326 (M+,
0.37), 214 (10.0), 119 (100), 91 (20). Anal. Calcd for C22H30O2:
C, 80.94; H, 9.26. Found: C, 80.86; H, 9.36.
Deter m in a tion th e Absolu te Con figu r a tion of 7b
P r ep a r a tion of Ester 9. A solution of 7b (805 mg, 1.70
mmol) and concentrated sufuric acid (0.2 mL) in methyl alcohol
(30 mL) was refluxed for 25 h. The resulting solution was
P r ep a r a tion of Acid 14.13 A solution of 13 (114 mg, 0.35
mmol) and potassium hydroxide (393 mg, 7.0 mmol) in methyl
alcohol (5 mL) was refluxed for 10 h. After concentration, to

5722 J . Org. Chem., Vol. 66, No. 17, 2001
Ye et al.
the residue was added water (10 mL). The resulting mixture
was acidified with 10% HCl and extracted with ethyl acetate.
The extraction was dried over Na2SO4. After concentration,
the residue was purified by column chromatography. Yield:
72%. [R]20 ) +107° (c ) 0.7, EtOH), (ref:11 [R]20 ) 165°, c )
2.0, EtOH); H NMR (300 MHz, CDCl3, TMS) δ 5.5-5.3 (m,
1H), 5.18 (d, J ) 16.0 Hz, 1H), 5.02 (d, J ) 10.0 Hz, 1H), 2.2-
2.0 (m, 1H), 1.7-1.6 (m, 1H), 15-1.4 (m, 1H), 1.1-1.0 (m, 1H).
Som e Ch em ica l Tr a n sfor m a tion s of th e ((Tr im eth yl-
silyl)vin yl)cyclop r op a n e Der iva tive 7b′
passed through a short silica gel column, which was eluted
with ethyl acetate. Upon removal of the solvent under vacuum,
the residue was purified by column chromatrography. Yield:
90%. 94.9% ee (determined by HPLC: OD-H, n-hexane/2-
PrOH ) 200/1, 1 mL/min; tR ) 12.2 min (minor), 13.4 min
D
D
1
(major)). [R]20 ) +64° (c ) 1.17, CHCl3); 1H NMR (300 MHz,
D
CDCl3, TMS) δ 7.4-7.2 (m, 5H), 5.97 (d, J ) 18.5 Hz, 1H),
5.38 (dd, J ) 18.5, 8.8 Hz, 1H), 3.82 (s, 3H), 3.03 (dd, J ) 9.6,
5.4 Hz, 1H), 2.54 (dt, J ) 9.0, 4.6 Hz, 1H), 2.32 (t, J ) 4.9 Hz,
1H), 0.08 (s, 9H).
(1R,2R,3S)-2-P h en yl-3-((tr im eth ylsilyl)vin yl)cyclop r o-
p a n eca boxylic Acid (15). A solution of 7b′ (de ) 95%,
recrystallization of 7b from ethyl alcohol, 203 mg, 0.428 mmol)
and potassium hydroxide (482 mg, 26.6 mmol) in methyl
alcohol (10 mL) was refluxed for 5 h. After concentration, to
the residue was added water (12 mL). The resulting mixture
was acidified with 10% HCl and extracted with ethyl acetate.
The extraction was dried and concentrated. The residue was
purified by column chromatograph to give (-)-8-phenylmenthol
Meth yl (1R,2R,3S)-2-(2-Acylvin yl)-3-p h en ylcyclop r o-
p a n eca r boxyla te (17). A solution of 16 (50 mg, 0.18 mmol)
in 15 mL of dichloromethane was added over 1 h to a stirred
mixture of acetyl chloride (72 mg, 0.91 mmol) and aluminum
chloride (121 mg, 0.91 mmol) in 8 mL of dichlormethane at 0
°C. The mixture was stirred for an additional 15 min and
poured into 20 mL of saturated sodium bicarbonate solution.
The aqueous layer was extracted with dichloromethane (3 ×
20 mL), and the combined organic layers were washed with
saturated sodium bicarbonate solution, dried over Na2SO4, and
evaporated. The residue was purified by column chromatog-
raphy to give 32 mg (72%) of the unsaturated ketone 17, 94.3%
ee (determined by HPLC: OD-H, n-hexane/2-PrOH ) 95/5, 0.8
(94 mg, 92%) and acid 15. Yield: 84%. mp 116-118 °C; [R]20
D
) +62° (c ) 1.0, CHCl3); IR (film) ν/cm-1 3207 (s, br), 1714
1
(vs), 1615 (m), 1440 (s), 1177 (s); H NMR (300 MHz, CDCl3,
TMS) δ 7.4-7.2 (m, 5H), 5.99 (d, J ) 18.5 Hz, 1H), 5.37 (dd,
J ) 18.5, 8.8 Hz, 1H), 3.08 (dd, J ) 9.6, 5.3 Hz, 1H), 2.60 (dt,
J ) 9.2, 4.4 Hz, 1H), 2.31 (t, J ) 4.9 Hz, 1H), 0.08 (s, 9H); MS
(EI, m/ z, rel intensity) 260 (M+, 3.90), 245 (41.87), 227 (17.64),
170 (39.44), 142 (100). Anal. Calcd for C15H20O2Si: C, 69.18;
H, 7.74. Found: C, 69.01; H, 7.36.
Meth yl (1R,2R,3S)-2-P h en yl-3-((tr im eth ylsilyl)vin yl)-
cyclop r op a n eca r boxyla te (16).8b To a solution of acid 15
(76 mg, 0.292 mmol), methyl alcohol (18 mg, 0.58 mmol), and
DMAP (36 mg, 0.20 mmol) in dichloromethane (4 mL) at 0 o C
was added DCC (120 mg, 0.58 mmol) in dichloromethane (2
mL). Then, the reaction mixture was allowed to warm to room
temperature. After stirring for 10 h, the reaction mixture was
mL/min; tR ) 19.8 min (major), 22.7 min (minor)). [R]20
)
D
+114.6° (c ) 1.0, CHCl3); IR (film) ν/cm-1 3031 (w), 2954 (w),
1733 (vs), 1671 (vs), 1444 (s), 1174 (s); 1H NMR (300 MHz,
CDCl3, TMS) δ 7.4-7.2 (m, 5H), 6,28 (d, J ) 15.8 Hz, 1H),
6.05 (dd, J ) 15.8, 10.1 Hz, 1H), 3.77 (s, 3H), 3.16 (dd, J )
9.3, 5.6 Hz, 1H), 2.55 (dt, J ) 9.8, 3.9 Hz, 1H), 2.42 (t, J ) 4.5
Hz, 1H), 2.05 (s, 3H); MS (EI, m/ z, rel intensity) 245 (M+,
3.23), 244 (1.59), 185 (32.32), 169 (20.34), 115 (34.89), 43 (100).
Anal. Calcd for C15H16O3: C, 73.75; H, 6.60. Found: C, 73.77;
H, 6.65.
J O010121X