Taniguchi Hiroki, Ohmura Toshimichi, Suginome Michinori
Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Kyoto 615-8510, Japan.
J Am Chem Soc. 2009 Aug 19;131(32):11298-9. doi: 10.1021/ja9046894.
A nickel-catalyzed intermolecular hydroacylation of methylenecyclopropanes (MCPs) has been developed. The reaction proceeds with stereospecific cleavage of the proximal C-C bond of the cyclopropane ring to give gamma,delta-unsaturated ketones with high diastereoselectivities. A nickel catalyst generated in situ from Ni(cod)(2) and P(n-Bu)(3) with a P/Ni ratio of 1:1 is effective for the hydroacylation, in which benzaldehyde derivatives, heteroaryl aldehydes, and aliphatic aldehydes react with MCPs at 60-100 degrees C to afford the corresponding ketones in high yields.
已开发出一种镍催化的亚甲基环丙烷（MCPs）分子间氢酰化反应。该反应通过环丙烷环近端C-C键的立体特异性裂解进行，以高非对映选择性生成γ,δ-不饱和酮。由Ni(cod)₂和P(n-Bu)₃原位生成的P/Ni比为1:1的镍催化剂对氢酰化反应有效，其中苯甲醛衍生物、杂芳基醛和脂肪醛在60-100℃下与MCPs反应，以高产率得到相应的酮。
