Department of Chemistry, South University of Science and Technology of China (SUSTC).; Center of Novel Functional Molecules, Shenzhen Research Institute, The Chinese University of Hong Kong (CUHK)..
Angew Chem Int Ed Engl. 2015 Apr 7;54(15):4512-6. doi: 10.1002/anie.201411882. Epub 2015 Feb 5.
An asymmetric tail-to-tail cross-hydroalkenylation of vinylarenes with terminal olefins was achieved by catalysis with NiH complexes bearing chiral N-heterocyclic carbenes (NHCs). The reaction provides branched gem-disubstituted olefins with high enantioselectivity (up to 94 % ee) and chemoselectivity (cross/homo product ratio: up to 99:1). Electronic effects of the substituents on the vinylarenes and on the N-aryl groups of the NHC ligands, but not a π,π-stacking mechanism, assist the steric effect and influence the outcome of the cross-hydroalkenylation.
镍氢配合物负载手性氮杂环卡宾(NHCs)催化实现了末端烯烃与乙烯基芳烃的不对称尾对尾交叉氢烯基化反应。该反应提供支化的偕二取代烯烃,具有高对映选择性(高达 94%ee)和化学选择性(交叉/同系物产物比:高达 99:1)。乙烯基芳烃和 NHC 配体的 N-芳基上取代基的电子效应,但不是π,π-堆积机理,辅助了空间效应并影响了交叉氢烯基化反应的结果。