1676 Bull. Chem. Soc. Jpn., 78, No. 9 (2005)
Radical Addition of Cyanoacetates to Alkenes
Linker, K. Peter, E. Peter, and. G. von Schnering, Synlett, 1996,
468. g) ‘‘Organic Synthesis by Oxidation with Metal Com-
pounds,’’ ed by W. J. Migs and C. R. H. I. de Jonge, Plenam Press,
New York (1986). h) M. Hajek and J. Malek, Synthesis, 1976, 315.
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In conclusion, we have observed a remarkable effect of
bases, like AcOK and amines, on the radical addition of 1a
to alkenes and dienes by using a Mn(II)/Co(II)/O2 redox
couple. This method provides an alternative route to the reac-
tion between enolates and electrophiles, like alkyl halides,
under mild conditions.
Experimental
2
a) W. E. Fristad and J. R. Peterson, J. Org. Chem., 50, 10
(1985). b) W. E. Fristad, J. R. Peterson, and A. B. Arnst, J. Org.
Chem., 50, 3143 (1985). c) L. Lamarque, A. Meou, and P. Brun,
Tetrahedron, 54, 6497 (1998).
All starting materials were commercially available and used
without any purification. GLC analysis was performed with a
flame ionization detector using a 0:2 mm ꢄ 25 m capillary column
(OV-1). 1H and 13C NMR were measured at 270 MHz and 67.5
MHz, respectively, in CDCl3 with Me4Si as the internal standard.
A typical reaction procedure: To a solution of 1 (60 mmol),
Mn(OAc)2 4H2O (0.06 mmol, 2.0 mol %), and Co(OAc)2
4H2O (0.03 mmol, 1.0 mol %) in a two-necked flask equipped
with a balloon filled with an appropriate concentration of O2
was added 2 (1 mmol); the mixture was stirred at room tempera-
ture for 5 h. The product was isolated by column chromatography
(230–400 mesh silica gel, hexane:ethyl acetate = 1:1). The con-
versions and yields of products were estimated from the peak
areas based on the internal standard technique using GLC.
Compounds 3aa,10 3ab,11 3ac,12 3ad,12 3af,13 3ah,14 and 3ba7
were reported previously.
3
a) A. Yamada, Y. Iwahara, H. Nishino, and K. Kurosawa,
J. Chem. Soc., Perkin Trans. 1, 1993, 609. b) C.-Y. Qian, T.
Yamada, H. Nishino, and K. Kurosawa, Bull. Chem. Soc. Jpn.,
65, 1371 (1992). c) V.-H. Nguyen, H. Nishino, and K. Kurosawa,
Tetrahedron Lett., 37, 4949 (1996). d) V.-H. Nguyen, H. Nishino,
and K. Kurosawa, Tetrahedron Lett., 38, 1773 (1997).
4 T. Ohshima, M. Sodeoka, and M. Shibasaki, Tetrahedron
Lett., 34, 8509 (1993).
5 L. Lamarque, A. Meou, and P. Brun, Can. J. Chem., 78,
128 (2000).
6 T. Iwahama, S. Sakaguchi, and Y. Ishii, Chem. Commun.,
2000, 2317.
7 K. Hirase, T. Iwahama, S. Sakaguchi, and Y. Ishii, J. Org.
Chem., 67, 970 (2002).
ꢂ
ꢂ
8
3381.
9
M. Cazaux and R. Lalande, Bull. Soc. Chim. Fr., 1966,
This work was partially supported by a Grant-in-Aid
for Scientific Research (S) from the Ministry of Education,
Culture, Sports, Science and Technology (MEXT), Japan.
a) F. Basolo, R. D. Jones, and D. A. Summerville,
Chem. Rev., 79, 139 (1979). b) C. L. Wong, J. A. Switer, K. P.
Balakrishnan, and J. F. Endicott, J. Am. Chem. Soc., 102, 5511
(1980). c) R. S. Drago, J. P. Cannady, and A. Leslie, J. Am. Chem.
Soc., 102, 6014 (1980).
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