Nakao Yoshiaki, Yukawa Tomoya, Hirata Yasuhiro, Oda Shinichi, Satoh Jun, Hiyama Tamejiro
Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan.
J Am Chem Soc. 2006 Jun 7;128(22):7116-7. doi: 10.1021/ja060519g.
Allyl cyanides are found to add across alkynes in the presence of a nickel catalyst prepared from Ni(cod)2 and P(4-CF3-C6H4)3 in situ to give variously functionalized di- or trisubstituted acrylonitriles in highly stereoselective manners possibly via a pi-allylnickel species as an intermediate. alpha-Siloxyallyl cyanides also react at the gamma-position of a cyano group with both internal and terminal alkynes having various functional groups to give silyl enol ethers, which give the corresponding aldehydes or ketones upon hydrolysis.
已发现烯丙基氰化物在由Ni(cod)2和P(4-CF3-C6H4)3原位制备的镍催化剂存在下与炔烃加成，以高度立体选择性的方式生成各种功能化的二取代或三取代丙烯腈，可能是通过π-烯丙基镍物种作为中间体。α-硅氧基烯丙基氰化物也会在氰基的γ位与具有各种官能团的内炔和端炔反应生成硅烯醇醚，硅烯醇醚水解后生成相应的醛或酮。
