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Nickel‐Catalyzed Migratory Hydrocyanation of Internal Alkenes: Unexpected Diastereomeric‐Ligand‐Controlled Regiodivergence
Author(s) -
Gao Jihui,
Jiao Mingdong,
Ni Jie,
Yu Rongrong,
Cheng GuiJuan,
Fang Xianjie
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202011231
Subject(s) - hydrocyanation , regioselectivity , steric effects , chemistry , diastereomer , catalysis , nickel , ligand (biochemistry) , nitrile , electronic effect , combinatorial chemistry , organic chemistry , biochemistry , receptor
A regiodivergent nickel‐catalyzed hydrocyanation of a broad range of internal alkenes involving a chain‐walking process is reported. When appropriate diastereomeric biaryl diphosphite ligands are applied, the same starting materials can be converted to either linear or branched nitriles with good yields and high regioselectivities. DFT calculations suggested that the catalyst architecture determines the regioselectivity by modulating electronic and steric interactions. In addition, moderate enantioselectivities were observed when branched nitriles were produced.