ORGANIC
LETTERS
2004
Vol. 6, No. 22
3917-3920
Highly (Z)-Selective Synthesis of
-Monosubstituted -Unsaturated
Cyanides Using the Peterson Reaction
â
r,â
Satoshi Kojima,*,†,‡ Tomohide Fukuzaki,† Atsushi Yamakawa,† and Yutaka Murai†
Department of Chemistry, Graduate School of Science,
and Center of Quantum Life Sciences, Hiroshima UniVersity, 1-3-1 Kagamiyama,
Higashi-Hiroshima 739-8526, Japan
Received July 10, 2004
ABSTRACT
The Peterson reaction between (t-BuO)Ph2SiCH2CN and various aldehydes furnishes the corresponding
â-monosubstituted r,â-unsaturated
cyanides with high Z selectivity (Z:E
) 92:8 to >98:2).
Since R,â-unsaturated carbonyl compounds are multifunc-
tional, they are considered to be versatile building blocks in
organic synthesis. For the efficient preparation of the
thermodynamically less stable disubstituted (Z)-olefins from
aldehydes, a few methods based upon Wittig-type1-5 and
Peterson-type6-8 reactions have been reported. The cyano
group functions similarly to carbonyls, but the inherent small
size of the substituent allows for chemistry of its own.9 As
for methods for the selective preparation of (Z)-R,â-unsatur-
ated cyanides, there are a few based upon phosphorus10,11
and silicon12,13 chemistry and there are interesting reports
that describe the use of cross-metathesis.14 Other than
multistep methods,13 however, reactions involving aromatic
aldehydes have been less successful, giving products with
only up to ca. 3:1 selectivity.
† Graduate School of Science, Hiroshima University.
Previously, we reported that R-triphenylsilylacetamides
(Ph3SiCH2CONR′2) were useful reagents for the preparation
‡ Center of Quantum Life Sciences, Hiroshima University.
(1) Still, W. C.; Gennari, C. Tetrahedron Lett. 1983, 24, 4405-4408.
(2) (a) Ando, K. Tetrahedron Lett. 1995, 36, 4105-4108. (b) Ando, K.
J. Org. Chem. 1997, 62, 1934-1939. (c) Ando, K. J. Org. Chem. 1998,
63, 8411-8416. (d) Ando, K. J. Org. Chem. 1999, 64, 8406-8408. (e)
Kokin, K.; Motoyoshiya, J.; Hayashi, S.; Aoyama, H. Synth. Commun. 1997,
27, 2387-2392.
(8) (a) Kojima, S.; Inai, H.; Hidaka, T.; Ohkata, K. Chem. Commun.
2000, 1795-1796. (b) Kojima, S.; Inai, H.; Hidaka, T.; Fukuzaki, T.;
Ohkata, K. J. Org. Chem. 2002, 67, 4093-4099.
(3) (a) Kojima, S.; Takagi, R.; Akiba, K.-y. J. Am. Chem. Soc. 1997,
119, 5970-5971. For related mechanistic studies, see: (b) Kojima, S.;
Akiba, K.-y. Tetrahedron Lett. 1997, 38, 547-550. (c) Kojima, S.;
Kawaguchi, K.; Akiba, K.-y. Tetrahedron Lett. 1997, 38, 7753-7756. (d)
Kojima, S.; Kawaguchi, K.; Matsukawa, S.; Akiba, K.-y. Tetrahedron 2003,
59, 255-265.
(4) Yu, W.; Su, M.; Jin, Z. Tetrahedron Lett. 1999, 40, 6725-6728.
(5) (a) Ando, K. Synlett 2001, 1272-1274. (b) Kojima, S.; Hidaka, T.;
Ohba, Y.; Ohkata, K. Phosphorus Sulfur Silicon 2002, 177, 729-732. (c)
Kojima, S.; Hidaka, T.; Ohba, Y. Heteroatom Chem. In press.
(6) For reviews on the Peterson reaction: (a) Ager, D. J. Synthesis
1984, 384-398. (b) Ager, D. J. Org. React. 1990, 42, 1-223. (c) van
Staden, L. F.; Gravestock, D.; Ager, D. J. Chem. Soc. ReV. 2002, 31, 195-
200.
(9) Fleming, F. F.; Wang, Q. Chem. ReV. 2003, 103, 2035-2077.
(10) Zhang, T. Y.; O’Toole, J. C.; Dunigan, J. M. Tetrahedron Lett. 1998,
39, 1461-1464.
(11) Kojima, S.; Kawaguchi, K.; Matsukawa, S.; Uchida, K.; Akiba, K.-
y. Chem. Lett. 2002, 170-171.
(12) (a) Yamakado, Y.; Ishiguro, M.; Ikeda, N.; Yamamoto, H. J.
Am. Chem. Soc. 1981, 103, 5568-5570. (b) Haruta, R.; Ishiguro, M.;
Furuta, K.; Mori, A.; Ikeda, N.; Yamamoto, H. Chem. Lett. 1982, 1093-
1096. (c) Furuta, K.; Ishiguro, M.; Haruta, R.; Mori, A.; Ikeda, N.;
Yamamoto, H. Bull. Chem. Soc. Jpn. 1984, 57, 2768-2776. (d) Palomo,
C.; Aizpurua, J. M.; Aurrekoetxea, N. Tetrahedron Lett. 1990, 31, 2209-
2210.
(13) (a) Sato, Y.; Niinomi, Y. J. Chem. Soc., Chem. Commun. 1982,
56-57. (b) Matsuda, I.; Okada, H.; Izumi, Y. Bull. Chem. Soc. Jpn. 1983,
56, 528-532.
(14) Crowe, W. E.; Goldberg, D. R. J. Am. Chem. Soc. 1995, 117, 5162-
5163; Randl, S.; Gessler, S.; Wakamatsu, H.; Blechert, S. Synlett 2001,
430-432.
(7) (a) Larcheveque, M.; Debal, A. J. Chem. Soc., Chem. Commun. 1981,
877-878. (b) Matsuda, I.; Izumi, Y. Tetrahedron Lett. 1981, 19, 1805-
1808. (c) Arai, S.; Tsuzuki, Y.; Matsuda, S.; Kitagaki, S.; Kita, Y. Synlett
1991, 911-912.
10.1021/ol0486728 CCC: $27.50
© 2004 American Chemical Society
Published on Web 09/25/2004