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Catalytic Asymmetric Hydroalkenylation of Vinylarenes: Electronic Effects of Substrates and Chiral N‐Heterocyclic Carbene Ligands
Author(s) -
Ho ChunYu,
Chan ChunWa,
He Lisi
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201411882
Subject(s) - chemoselectivity , carbene , steric effects , chemistry , catalysis , electronic effect , stacking , aryl , stereochemistry , medicinal chemistry , combinatorial chemistry , organic chemistry , alkyl
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.