Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan.
J Am Chem Soc. 2010 Jul 28;132(29):10070-7. doi: 10.1021/ja102346v.
Cyanoformates and cyanoformamides are found to add across alkynes by nickel/Lewis acid (LA) cooperative catalysis to give beta-cyano-substituted acrylates and acrylamides, respectively, in highly stereoselective and regioselective manners. The resulting adducts serve as versatile synthetic building blocks through chemoselective transformations of the ester, amide, and cyano groups as demonstrated by the synthesis of typical structures of beta-cyano ester, beta-amino nitrile, gamma-lactam, disubstituted maleic anhydride, and gamma-aminobutyric acid. The related reactions of cyanoformate thioester and benzoyl cyanide, on the other hand, are found to add across alkynes with decarbonylation in the presence of a palladium/LA catalyst.
氰基甲酸酯和氰基甲酰胺通过镍/路易斯酸（LA）协同催化被发现可以加成到炔烃上，分别以高度立体选择性和区域选择性的方式得到β-氰基取代的丙烯酸酯和丙烯酰胺。通过酯基、酰胺基和氰基的化学选择性转化，所得到的加成都可以作为多功能的合成砌块，这在β-氰基酯、β-氨基腈、γ-内酰胺、二取代马来酸酐和γ-氨基丁酸等典型结构的合成中得到了证明。另一方面，氰基甲酸酯硫代酯和苯甲酰基氰化物的相关反应在钯/LA 催化剂的存在下被发现可以与炔烃发生脱羰加成反应。
