Yang Bo, Wang Zhong-Xia
CAS Key Laboratory of Soft Matter Chemistry and Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, P. R. China.
Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300072, P. R. China.
J Org Chem. 2020 Apr 3;85(7):4772-4784. doi: 10.1021/acs.joc.0c00008. Epub 2020 Mar 19.
By choosing different phosphine ligands, nickel-catalyzed selective alkylation and reduction of allylic alcohols with alkyl Grignard reagents were performed. The reaction using Ni(dppe)Cl as the catalyst resulted in the cross-coupling of allylic alcohols with primary alkyl Grignard reagents and cyclopropylmagnesium bromide. The reaction catalyzed by the combination of Ni(PCy)Cl and dcype led to the reduction of allylic alcohols. Secondary alkyl Grignard reagents except cyclopropylmagnesium bromide always led to reduction of allylic alcohols using either Ni(dppe)Cl or Ni(PCy)Cl/dcype as the catalyst. In the reductive reaction β-H-containing alkyl Grignard reagents were required.
通过选择不同的膦配体，实现了镍催化的烯丙醇与烷基格氏试剂的选择性烷基化和还原反应。以Ni(dppe)Cl为催化剂的反应导致烯丙醇与伯烷基格氏试剂和环丙基溴化镁发生交叉偶联。由Ni(PCy)Cl和dcype组合催化的反应导致烯丙醇的还原。除环丙基溴化镁外，仲烷基格氏试剂在使用Ni(dppe)Cl或Ni(PCy)Cl/dcype作为催化剂时总是导致烯丙醇的还原。在还原反应中，需要含β-H的烷基格氏试剂。
