3966 J. Org. Chem.

2000, 65, 3966-3970

Isomerization Reaction of Olefin Using RuClH(CO)(PPh3)3

Hideaki Wakamatsu, Mayumi Nishida, Naoko Adachi, and Miwako Mori*

Graduate School of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan

Received December 6, 1999

When methyl 5-(tert-butyldiphenylsilyl)oxy-2-pentenoate was refluxed in toluene in the presence

of RuClH(CO)(PPh3)3 (5 mol %), double-bond migration took place to afford methyl 5-(tert-
butyldiphenylsilyl)oxy-4-pentenoate in high yield. This means that the double bond conjugated with
the ester moiety migrates to a deconjugated position by a ruthenium catalyst. We planned to prepare
an enol ether from R,β-unsaturated compounds having an ether moiety in a tether using ruthenium-
catalyzed isomerization of the double bond. As a result, silyl or benzyl enol ether was obtained
from the R,β-unsaturated ester having alcohol protected by the silyl or benzyl group in a tether in
high yield. In this reaction, double bond migration of R,β-unsaturated ketone and R,β-unsaturated
amide took place to produce deconjugated compounds. Moreover, the double bond of R,β-unsaturated
ester having a triple or double bond in a molecule migrated to produce conjugated enyne and diene.
On the other hand, treatment of a bis-metalated compound having an R,β-unsaturated ester moiety
or the double bond in a tether with RuClH(CO)(PPh3)3 gave allyl bis-metalated compound in good
yield. These compounds are useful units in synthetic organic chemistry.

It is known that the isomerization reaction proceeds Scheme 1

by acid, base, or organometallic complexes, and in
general, a thermodynamically stable product is produced.
Certain transition metal complexes, such as Fe, Pd, Rh,
Pt, Ni, Ir, Ru, and Cr, are known as the catalysts for
isomerization reaction.1 RuClH(CO)(PPh3)3 is also known
as a catalyst for isomerization, but the reaction usually Scheme 2. Our Plan for Isomerization
affords a mixture of olefin isomers and it has rarely been
used as an isomerization reagent in organic synthesis.
However, several interesting examples have been shown
in the literature.2
During the course of our study on ruthenium-catalyzed
of compound 2 was refluxed in the presence of 1.7 mol %
enyne cyclization,3 we found that when a toluene solution
of ruthenium catalyst 1 for 2 h, the double bond of R,β-
unsaturated ester 2 was isomerized to provide deconju-
(1) Fe: (a) Jolly, P. W.; Stone, F. G. A.; Mackenzie, K. J. Chem. Soc.
1965, 6416. (b) Cowherd, F. G.; von Rosenberg, J. L. J. Am. Chem. gated product 3 in high yield (Scheme 1).
Soc. 1969, 91, 2157. (c) Hubert, A. J.; Georis, A.; Warin, R.; Teyssié, Although R,β-unsaturated ester 2 is considered to be
P. J. Chem. Soc., Perkin Trans. 2 1972, 366. (d) Stille, J. K.; Becker, a thermodynamically stable compound compared with
Y. J. Org. Chem. 1980, 45, 2139. Pd: (e) Golborn, P.; Scheinmann, F.
J. Chem. Soc., Perkin Trans. 1 1973, 2870. Rh: (f) Corey, E. J.; Suggs, the deconjugated product 3, in this case, the double bond
J. W. J. Org. Chem. 1973, 38, 3224. (g) Strohmeier, W.; Weigelt, L. J. conjugated with the ester part moved to nonconjugated
Organomet. Chem. 1975, 86, C17. (h) Aresta, M.; De Fazio, M. J. part in the presence of ruthenium catalyst 1. Presumably,
Organomet. Chem. 1980, 186, 109. (i) Alper, H.; Hachem, K. J. Org.
Chem. 1980, 45, 2269. (j) Tani, K.; Yamagata, T.; Akutagawa, S.; the reaction would proceed through hydroruthenation
Kumobayashi, H.; Taketomi, T.; Takaya, H.; Miyashita, A.; Noyori, and then β-hydrogen elimination. We were very inter-
R.; Otsuka, S. J. Am. Chem. Soc. 1984, 106, 5208. (k) Nemoto, H.;
Jimenez, H. N.; Yamamoto, Y. J. Chem. Soc., Chem. Commun. 1990,
ested in these results although the reason was not clear.
1304, and 1d. Ni: (l) Lochow, C. F.; Miller, R. G. J. Org. Chem. 1976, We planned to synthesize functionalized compounds
41, 3020. Ir: (m) Baudry, D.; Ephritikhine, M.; Felkin, H. J. Chem. from R,β-unsaturated carbonyl compounds using ruthe-
Soc., Chem. Commun. 1978, 694. (n) Ohmura, T.; Shirai, Y.; Yama-
moto, Y.; Miyaura, N. Chem. Commun. 1998, 1337. Ru: (o) Suzuki, nium catalyst as shown in Scheme 2. If an R,β-unsatur-
H.; Koyama, Y.; Moro-oka, Y.; Ikawa, T. Tetrahedron Lett. 1979, 1415. ated carbonyl compound having a functional group at an
(p) Zoran, A.; Sasson, Y. J. Org. Chem. 1981, 46, 255. (q) Takahashi, appropriate position in a tether is treated with RuClH-
M.; Suzuki, H.; Moro-oka, Y.; Ikawa, T. Chem. Lett. 1981, 1435, and
1d. Cr: (r) Sodeoka, M.; Yamada, H.; Shibasaki, M. J. Am. Chem. Soc. (CO)(PPh3)3, the double bond would move from the R,β-
1990, 112, 4906. (s) Yamada, H.; Sodeoka, M.; Shibasaki, M. J. Org. position of the carbonyl group to the position conjugated
Chem. 1991, 56, 4569. Pt: (t) Clark, H. C.; Kurosawa, H. Inorg. Chem. with the functional group.
1973, 12, 357. (u) Clark, H. C.; Kurosawa, H. Inorg. Chem. 1973, 12,
1566.
(2) (a) Bingham, D.; Webster, D. E.; Wells, P. B. J. Chem. Soc., Isomerization of the Double Bond of
Dalton Trans. 1974, 1519. (b) Matsuda, I.; Kato, T.; Sato, S.; Izumi,
Y. Tetrahedron Lett. 1986 27, 5747. (c) Suzuki, H.; Yashima, H.; Hirose,
r,β-Unsaturated Carbonyl Compounds
T.; Takahashi, M.; Moro-oka, Y.; Ikawa, T. Tetrahedron Lett. 1980 21,
4927. (d) Hirai, K.; Suzuki, H.; Moro-oka, Y.; Ikawa, T. Tetrahedron When a toluene solution of 4a was refluxed in the
Lett. 1980, 21, 3413. (e) Hirai, K.; Suzuki, H.; Kashiwagi, H.; Moro- presence of 1 (5 mol %) for 2 h, silyl enol ether 5a was
oka, Y.; Ikawa, T. Chem. Lett. 1982, 23. (f) Hiraki, K.; Matsunaga, T. obtained in 97% yield (ratio E/Z: 1:2.1, Scheme 3).
Organometallics 1994, 13, 1878.
(3) Nishida, M.; Adachi, N.; Onozuka, K.; Matsumura, H.; Mori, M. R,β-Unsaturated esters, 4b-4f, having various carbon
J. Org. Chem. 1998, 63, 9158. chains were treated in a similar manner, and the desired
10.1021/jo9918753 CCC: $19.00 © 2000 American Chemical Society
Published on Web 05/24/2000
Isomerization Reaction of Olefin Using RuClH(CO)(PPh3)3 J. Org. Chem., Vol. 65, No. 13, 2000 3967

Scheme 3 Table 2. Isomerization of r,β-Unsaturated Estera

Table 1.a
run substrate n time (h) yield of 5 (%) E/Z
b
1 4b 1 2 94 1/2.2
2 4c 2 2 80 1/2.2
3 4d 3 2 85 1/2.2
4 4e 4 4 78 1/2.0
5 4f 5 4 74 1/2.1
a The ratios are determined by 1H NMR.

Scheme 4

silyl enol ethers 5b-5f were obtained in good yields

(Table 1). These results indicated that the double bond a All reactions were carried out in toluene upon refluxing for 2
in R,β-unsaturated esters moved into a position conju-
h in the presence of RuClH(CO)(PPh3)3 (5 mol %). b Starting
gated with the silyl ether (Scheme 4). material was recovered in 23% yield. c The reaction time was
Subsequently, isomerization of the double bond of R,β- 24 h.
unsaturated carbonyl compounds having various func-
Scheme 5. Synthesis of Bis-Stannylated
tional groups was carried out. From R,β-unsaturated
Compound Having Olefin in a Tether
ester 4g having the benzyloxy group in a molecule, benzyl
enol ether 5g was obtained in high yield (Table 2, run
1). These results indicate that compounds having R,β-
unsaturated ester and the hydroxyl group protected by
the various groups in a molecule could be converted into
compounds having saturated ester and the enol ether. Scheme 6. Plan for Isomerization of
Bis-Stannylated Compound
As the functional moiety, alkyne or alkene can be used,
and 1,3-ynene 5h and 1,3-diene 5i were produced in good
yields (runs 2 and 3). The isomerization of the double
bond of R,β-unsaturated amide 4j and ketone 4k also
proceeded smoothly to give saturated amide 5j and
ketone 5k in 78% and 79% yields, respectively (runs 4
and 5). In the case of R,β-unsaturated ketone, the reaction
time is longer than that of R,β-unsaturated ester or amide
because of the strong coordination of the keto-carbonyl organic synthesis, in high yield.4 If compound 8, which
group to the ruthenium metal. would be synthesized from 7, can be converted into the
allyl bis-stannylated compound 9, it would be used as an
These results indicated that olefin isomerization of R,β-
equivalent with 1,3-dianion 10 (Schemes 5 and 6). The
unsaturated carbonyl compounds proceeded smoothly
synthesis of allyl bis-stannylated compounds is quite
using a catalytic amount of RuClH(CO)(PPh3)3 to give
difficult, and there have only been a few reports on such
deconjugated carbonyl compounds in good yields and that
synthesis.5
R,β-unsaturated carbonyl compounds having the func-
The starting bis-metalated compounds 8a (n ) 0) and
tional group in a tether could be converted into useful
8b (n ) 1) having an R,β-unsaturated ester in a tether
precursors for organic synthesis.
were synthesized from bis-stannylated compound 7 by
the usual method, respectively (Scheme 7).
Synthesis of Allyl Bis-Metalated Compounds
(4) (a) Mori, M.; Kaneta, N.; Isono, N.; Shibasaki, M. Tetrahedron
Subsequently, we tried to synthesize allyl bis-meta- Lett. 1991, 32, 6139. (b) Isono, N.; Mori, M. Tetrahedron Lett., 1995,
36, 9345. (c) Isono, N.; Mori, M. J. Org. Chem. 1996, 61, 7867. (d) Isono,
lated compounds from bis-metalated compounds having N.; Mori, M. J. Org. Chem. 1998, 63, 1773. (e) Wakamatsu, H.; Isono.
an R,β-unsaturated ester part. We have already shown N.; Mori, M. J. Org. Chem. 1997, 62, 8917.
that the reaction of methyl propiolate 6 with Me3SiSnBu3 (5) (a) Reich, H. J.; Ringer, J. W. J. Org. Chem. 1988, 53, 455. (b)
Lautens, M.; Huboux, A. H.; Chin, B.; Downer, J. Tetrahedron Lett.
in the presence of BnEt3NCl gave methyl bis(tributyl- 1990, 31, 5829. (c) Madec, D.; Férézou, J.-P. Tetrahedron Lett. 1997,
stannyl)propionate 7, which is a useful C-3 unit for 38, 6657.
3968 J. Org. Chem., Vol. 65, No. 13, 2000 Wakamatsu et al.

Scheme 7a Scheme 8

a Key: (i) (COCl) , DMSO; (ii) Ph +CH OCH Cl-, t-BuOK; (iii)
2 3 2 3
concd HCl aq, MeOH; (iv) 2 N H2SO4; (v) Ph3PdCHCOOMe; (vi)
NaBH4, cat. NiCl2, MeOH; (vii) LiAlH4, THF; (viii) Ph3PCH2.

Table 3. Synthesis of Allyl Bis-Metalated Compounda

compounds using RuClH(CO)(PPh3)3. Although these bis-

metalated compounds are a mixture of E- and Z-isomers,
it has been known that the reaction of a mixture of E-
and Z-isomers of allylstannane with aldehyde gave a
single coupling product.6

The Reactivity of Allyl Bis-Metalated Compound

To examine the reactivity of allyl bis-metalated com-
pound 9, the reaction of 9 with aldehyde was carried out.
Compound 9b was reacted with benzaldehyde in the
presence of BF3‚Et2O to give vinyl stannane. The crude
product 15b was treated with I2 followed by PCC oxida-
tion to give vinyl iodide 16 in good yield. Compound 9f
was treated with benzaldehyde in the presence of BF3‚
Et2O to give vinyl germanium compound 15f in 97%
yield, which was converted into ketone 17 having vinyl
germanium moiety. Furthermore, intramolecular cycliza-
tion of 9b was attempted. Treatment of 9b with DIBAL-H
followed by acid workup surprisingly gave the cyclized
a All reactions were carried out under reflux in toluene for 2-30
product 18 in one step. Probably, the reduction of 9b with
h in the presence of 1 (5 mol %). The ratio (E/Z) of 9 is 1/1. DIBAL-H gives 20 and the allyl stannyl moiety reacts
with the acetal part of 20 to give 18. To determine the
When a toluene solution of 8a was refluxed in the stereochemistry of the cyclized product, compound 18 was
presence of a catalytic amount of 1 (5 mol %), allyl bis- treated with I2 to give vinyl iodide 19, whose NOE
stannylated compound 9a was obtained in 80% yield experiment indicated that trans-1,2-cyclopentanol was
(Table 3, run 1). In a similar manner, compound 8b gave formed. These results indicate that allyl bis-metalated
9b in 86% yield (run 2). Since we have been very compound can react as an equivalent with 1,3-dianion
interested in these allyl bis-stannylated compounds 9a 10.
and 9b, we examined to synthesize various allyl bis- In summary, we found that olefin isomerization of R,β-
metalated compounds from bis-metalated compounds unsaturated carbonyl compounds proceeded smoothly
8c-f having the olefin moiety in a tether. Bis-metalated using a catalytic amount of RuClH(CO)(PPh3)3 to give
compound 8c was prepared from 11a in a usual manner deconjugated carbonyl compounds in good yields and that
(Scheme 7), and 8d-f were synthesized as follows R,β-unsaturated ester having a functional group in a
(Scheme 8). Reaction of 11a with t-BuMe2SiCl or Et3SiCl tether could be converted into a useful precursor for
gave silyl ether 12d or 12e, which was treated with BuLi
to give silyl-stannylated compound 11d or 11e via 13.4d (6) (a) Yamamoto, Y.; Yatagai, H.; Naruta, Y.; Maruyama, K. J. Am.
Chem. Soc. 1980, 102, 7107. (b) Yamamoto, Y.; Yatagai, H.; Ishihara,
Germylated compound 11f was prepared from 11a. Y.; Maeda, N.; Maruyama, K. Tetrahedron 1984, 40, 2239. For another
Protection of the hydroxy group of 11a with MOMCl study of the stereochemistry in the reaction of allylstannane with
followed by treatment with BuLi and then Me3GeCl in aldehyde, see: (c) Marshall, J. A.; Welmaker, G. S. J. Org. Chem. 1992,
57, 7158. (d) Keck, G. E.; Abbott, D. E.; Boden, E. P.; Enholm, E. J.
the presence of HMPA gave 14. Deprotection of the MOM Tetrahedron Lett. 1984, 25, 3927. (e) Keck, G. E.; Abbott, D. E.
group with concd HCl in MeOH afforded 11f. Compounds Tetrahedron Lett. 1984, 25, 1883. (f) Gevorgyan, V.; Kadota, I.;
11d-f were converted into 8d-f in the usual manner. Yamamoto, Y. Tetrahedron Lett. 1993, 34, 1313. (g) Denmark, S. E.;
Weber, E. J. J. Am. Chem. Soc. 1984, 106, 7970. (h) Denmark, S. E.;
The isomerization reaction of bis-metalated compounds Weber, E. J.; Wilson, T. M.; Willson, T. M. Tetrahedron 1989, 45, 1053.
8c-f also proceeded smoothly in the presence of 1 in (i) Denmark, S. E.; Hosoi, S. J. Org. Chem. 1994, 59, 5133. (j) Keck,
toluene upon heating to give allyl bis-metalated com- G. E.; Dougherty, S. M.; Savin, K. A. J. Am. Chem. Soc. 1995, 117,
6210. (k) Koreeda, M.; Tanaka, Y. Chem Lett. 1982, 1297. (l) Koreeda,
pounds 9c-f in high yields, respectively. (Table 3, runs M.; Tanaka, Y. Tetrahedron Lett. 1987, 28, 143. (m) Hoffman, R. W.
3-6). Thus, we could obtain various 1,1-bis-metalated Chem. Rev. 1989, 89, 1841.
Isomerization Reaction of Olefin Using RuClH(CO)(PPh3)3 J. Org. Chem., Vol. 65, No. 13, 2000 3969

Scheme 9 Methyl 5-((E)-2-Iodovinyl)-6-oxo-6-phenylhexanoate

(16). To a solution of PhCHO (3 µL, 0.03 mmol) in CH2Cl2 was
added BF3‚OEt2 (4 µL, 0.03 mmol) at -78 °C, and the solution
was stirred for 5 min. To this solution were added 9b (21.1
mg, 0.03 mmol) and BF3‚OEt2 (11.0 µL, 0.09 mmol). The
resulting solution was stirred for 30 min at the same temper-
ature. Saturated NaHCO3 solution was added, and the aque-
ous phase was extracted with Et2O. The organic phase was
washed with brine, dried over Na2SO4, filtered, and concen-
trated. The crude product was dissolved in CCl4 and cooled to
0 °C. To this solution was added I2 (excess) in CCl4 until the
reddish brown color was not consumed. The resulting solution
was evaporated, and the residue was purified by column
chromatography on silica gel (4:1-5:1 hexane/AcOEt) to
provide a mixture of iodovinyl derivative. The product was
dissolved in CH2Cl2 and cooled to 0 °C. To this solution were
added MS4A (53.6 mg, powdered) and PCC (13.4 mg, 0.06
mmol). After the solution was stirred for 1 h at room temper-
ature, Et2O was added. The solution was passed through the
Florisil tube and was evaporated. The residue was purified
by column chromatography on silica gel (10:1 hexane/AcOEt)
to provide a colorless oil of 16 (8.2 mg, 75%): IR (neat) 1736,
1682 cm-1; 1H NMR (500 MHz, CDCl3) δ 1.59-1.72 (m, 3 H),
1.84-1.94 (m, 1 H), 2.33 (t, J ) 7.1 Hz, 2 H), 3.65 (s, 3 H),
4.07-4.11 (m, 1 H), 6.30 (d, J ) 14.6 Hz, 1 H), 6.63 (dd, J )
9.0, 14.6 Hz, 1 H), 7.48 (dd, J ) 7.1, 7.4 Hz, 2 H), 7.59 (t, J )
7.4 Hz, 1 H), 7.93 (d, J ) 7.1 Hz, 2 H); 13C NMR (125 MHz,
CDCl3) δ 22.5 (CH2), 31.2 (CH2), 33.7 (CH2), 51.6 (CH3), 53.3
(CH), 78.4 (CH), 128.4 (CH), 128.8 (CH), 133.5 (CH), 136.2 (C),
143.5 (CH), 173.5 (C), 198.5 (C); MS m/z 372 (M+), 341, 245,
organic synthesis. Moreover, allyl bis-metalated com-
105, 77; HRMS m/z calcd for C15H17O3I (M+) 372.0223, found
pounds could be synthesized from the corresponding 372.0220.
bis-metalated compounds having the double bond in a (E)-2-Methyl-4-(trimethylgermyl)-1-phenyl-3-buten-1-
tether. ol (15f). To a solution of PhCHO (10 µL, 0.10 mmol) in CH2-
Cl2 (0.9 mL) was added BF3‚OEt2 (12 µL, 0.10 mmol) at -78
Experimental Section °C, and the solution was stirred for 5 min. To this solution
was added 9f (40.8 mg, 0.09 mmol) in CH2Cl2 (0.9 mL) and
General Methods. Solvents were distilled under an argon BF3‚OEt2 (33 µL, 0.26 mmol). The resulting solution was
atmosphere from sodium benzophenone (THF), CaH2 (CH2Cl2, stirred for 30 min at the same temperature. Saturated
CCl4), and LiAlH4 (toluene). All other reagents were purified NaHCO3 solution was added, and the aqueous phase was
when necessary by standard procedures. All reactions were extracted with Et2O. The organic phase was washed with
conducted under an argon atmosphere. 1H NMR spectra were brine, dried over Na2SO4, filtered, and concentrated. The
recorded at 500 MHz. 13C NMR spectra were recorded at 125 residue was purified by column chromatography on silica gel
MHz. 1H NMR and 13C NMR shifts (ppm) were reported (3:1:0.04 hexane/AcOEt/Et3N) to provide a colorless oil of 15f
relative to internal tetramethylsilane (Me4Si). For 13C NMR (23.9 mg, 97%): IR (neat) 3412, 1612, 1236 cm-1; 1H NMR (500
spectra, carbon type is defined as (CH3), (CH2), (CH), or (C) MHz, CDCl3) δ 0.14 (s, 0.60 × 9 H), 0.21 (s, 0.40 × 9 H), 0.86
on basis of DEPT experiments. 119Sn NMR spectra were (d, J ) 6.8 Hz, 0.40 × 3 H), 1.00 (d, J ) 6.8 Hz, 0.60 × 3 H),
recorded at 100 MHz. 119Sn NMR shifts (ppm) were reported 1.93 (d, J ) 3.6 Hz, 0.60 × 1 H), 2.16 (d, J ) 2.4 Hz, 0.40 × 1
relative to external tetramethyltin (Me4Sn). H), 2.43-2.51 (m, 0.40 × 1 H), 2.55-2.60 (m, 0.60 × 1 H),
General Procedure for Isomerization Reaction by a 4.35 (dd, J ) 2.4, 8.0 Hz, 0.40 × 1 H), 4.62 (dd, J ) 3.6, 5.4
Ruthenium Catalyst. A toluene solution of 2, 4, or 8 (0.1 M) Hz, 0.60 × 1 H), 5.83-5.84 (m, 0.60 × 2 H), 5.88 (dd, J ) 7.7,
and RuClH(CO)(PPh3)3 (1) (5 mol %) was refluxed for 2-30 h. 18.3 Hz, 0.40 × 1 H), 6.00 (d, J ) 18.3 Hz, 0.40 × 1 H), 7.24-
After the solvent was removed, the residue was purified by 7.33 (m, 5 H); MS m/z 265 (M+ - Me + 1), 247, 225, 174, 159,
column chromatography on silica gel to provide 3, 5, or 9. 119, 107; HRMS m/z calcd for C13H19OGe (M+ - Me) 265.0648,
Methyl 5-(tert-butyldiphenylsilyl)oxy-4-pentenoate found 265.0639.
(5a): IR (neat) 1740, 1660, 1428, 1114 cm-1; 1H NMR (500 (E)-2-Methyl-4-(trimethylgermyl)-1-phenyl-3-buten-1-
MHz, CDCl3) δ 1.06 (s, 0.32 × 9 H), 1.09 (s, 0.68 × 9 H), 2.15 one (17). To a solution of 15f (7.5 mg, 0.03 mmol) in CH2Cl2
(dt, J ) 7.4, 7.5 Hz, 0.32 × 2 H), 2.27 (t, J ) 7.4 Hz, 0.32 × 2 (1.0 mL) were added MS4A (46.4 mg, powdered) and PCC (11.6
H), 2.44 (dd, J ) 7.4, 7.6 Hz, 0.68 × 2 H), 2.57 (ddd, J ) 6.9, mg, 0.05 mmol) at 0 °C, and the solution was stirred for 3 h at
7.4, 7.6 Hz, 0.68 × 2 H), 3.59 (s, 0.32 × 3 H), 3.68 (s, 0.68 × 3 the same temperature. This reaction mixture was diluted with
H), 4.49 (dt, J ) 5.6, 6.9 Hz, 0.68 × 1 H), 5.08 (dt, J ) 11.9, Et2O, subjected to column chromatography on Florisil, and
7.5 Hz, 0.32 × 1 H), 6.20 (d, J ) 5.6 Hz, 0.68 × 1 H), 6.30 (d, concentrated. The residue was purified by column chromatog-
J ) 11.9 Hz, 0.32 × 1 H), 7.36-7.67 (m, 10 H); MS m/z 368 raphy on silica gel (1:1 hexane/benzene) to provide a colorless
(M+), 353, 337, 311, 269, 213; HRMS m/z calcd for C22H28O3Si oil of 17 (7.0 mg, 95%): IR (neat) 1684, 1448, 1222 cm-1; 1H
(M+) 368.1808, found 368.1804. NMR (500 MHz, CDCl3) δ 0.15 (s, 9 H), 1.32 (d, J ) 6.8 Hz, 3
Methyl 6,6-bis(tributylstannyl)-4-hexenoate (9a): IR H), 4.19 (dq, J ) 6.7, 6.8 Hz, 1 H), 5.99 (d, J ) 18.4 Hz, 1 H),
(neat) 1744, 1464 cm-1; 1H NMR (500 MHz, CDCl3) δ 0.75- 6.06 (dd, J ) 6.7, 18.4 Hz, 1 H), 7.45 (dd, J ) 7.5, 7.5 Hz, 2
0.91 (m, 30 H), 1.26-1.52 (m, 24 H), 1.78 (d, J ) 12.2 Hz, 0.5 H), 7.55 (dd, J ) 7.5, 7.5 Hz, 1 H), 7.98 (d, J ) 7.5 Hz, 2 H);
13C NMR (125 MHz, CDCl ) δ -1.9 (CH ), 17.2 (CH ), 48.0
× 1 H, 2J (119Sn-1H) ) 27.2 Hz), 1.99 (d, J ) 14.3 Hz, 0.5 × 3 3 3
1 H, 2J (119Sn-1H) ) 25.7 Hz), 2.16-2.34 (m, 4 H), 3.66 (s, 0.5 (CH), 128.5 (CH), 128.6 (CH), 132.8 (CH), 133.4 (CH), 136.6
× 3 H), 3.67 (s, 0.5 × 3 H), 4.83-4.87 (m, 0.5 × 1 H), 5.02- (C), 143.3 (CH), 201.3 (C); MS m/z 277 (M+), 263, 159, 119,
5.08 (m, 0.5 × 1 H), 5.53-5.68 (m, 1 H); 119Sn NMR (100 MHz, 105, 77; HRMS m/z calcd for C14H20OGe (M+) 278.0726, found
CDCl3) δ -4.3, -4.2; MS m/z 706 (M+), 649 (M+ - Bu), 417, 278.0712.
361, 291, 235, 179; HRMS m/z calcd for C31H64O2Sn2 (M+) trans-2-((E)-2-(Tributylstannyl)vinyl)-1-cyclopen-
708.2950, found 708.2953. tanol (18). To a solution of 9b (44.3 mg, 0.06 mmol) in toluene
3970 J. Org. Chem., Vol. 65, No. 13, 2000 Wakamatsu et al.

(1.0 mL) was added DIBAL-H in toluene solution (0.18 mL, aqueous phase was extracted with Et2O. The organic phase
0.18 mmol, 1.01 M) at -78 °C. After the reaction mixture was was washed with brine, dried over Na2SO4, filtered, and
stirred for 30 min at the same temperature, CH3OH (0.1 mL) concentrated. The residue was purified by column chromatog-
was added. The resulting solution was poured into 1 N HCl raphy on silica gel (10:1 hexane/AcOEt) to provide a colorless
solution and extracted with Et2O. The organic phase was oil of 19 (8.3 mg, 72%): IR (neat) 3342, 1602 cm-1; 1H NMR
washed with brine, dried over Na2SO4, filtered, and concen- (500 MHz, CDCl3) δ 1.45 (ddd, J ) 9.0, 12.9, 17.1 Hz, 1 H),
trated. The residue was purified by column chromatography 1.53-1.69 (m, 3 H), 1.72-1.80 (m, 1 H), 1.90-2.04 (m, 2 H),
on silica gel (10:1 hexane/AcOEt) to provide a colorless oil of 2.37 (dddd, J ) 8.0, 8.1, 8.2, 8.5 Hz, 1 H), 3.90-3.95 (m, 1 H),
18 (16.9 mg, 68%, trans/cis ) 8.5/1): IR (neat) 3346 cm-1; 1H 6.12 (d, J ) 14.3 Hz, 1 H), 6.47 (dd, J ) 8.5, 14.3 Hz, 1 H); 13C
NMR (500 MHz, CDCl3) δ 0.76-0.91 (m, 15 H), 1.27-1.77 (m, NMR (125 MHz, CDCl3) δ 21.1 (CH2), 29.1 (CH2), 33.5 (CH2),
16 H), 1.91-1.99 (m, 2 H), 2.36 (ddt, J ) 7.1, 7.4, 7.9 Hz, 1 55.1 (CH), 75.3 (CH), 77.6 (CH), 148.1 (CH); MS m/z 238 (M+),
H), 3.61-3.66 (m, 0.11 × 1 H), 3.88-3.92 (m, 0.89 × 1 H), 180, 167, 154, 127, 111, 93; HRMS m/z calcd for C7H11OI (M+)
5.87 (dd, J ) 7.1, 18.9 Hz, 1 H), 5.98 (d, J ) 18.9 Hz, 1 H); 237.9855, found 237.9869.
119
Sn NMR (100 MHz, CDCl3) δ -49.0; MS m/z 345 (M+ -
Bu + 1), 289, 233, 177; HRMS m/z calcd for C15H29OSn (M+ - Supporting Information Available: 1H NMR, 13C NMR
Bu) 345.1240, found 345.1231. IR, and MASS spectral data of compounds 4e,f, 4h-k, 5b-k,
trans-2-((E)-2-Iodovinyl)-1-cyclopentanol (19). To a so- and 9b-f. Experimental procedures for 8a-f, 11e, 12e, and
lution of 18 (19.5 mg, 0.05 mmol) in CCl4 (2.0 mL) was added 14. This material is available free of charge via the Internet
I2 (excess) in CCl4 solution at 0 °C until the reddish brown at http://pubs.acs.org.
color was not consumed. The resulting solution was diluted
with Et2O, and 10% aqueous NH4OH solution was added. The JO9918753