Premium
Theoretical mechanistic study of nickel‐catalyzed anti‐Markovnikov hydroarylation of alkenes
Author(s) -
Li Jing,
Guan Wei
Publication year - 2021
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.26621
Subject(s) - markovnikov's rule , chemistry , reductive elimination , catalysis , oxidative addition , combinatorial chemistry , aryl , medicinal chemistry , organic chemistry , regioselectivity , alkyl
Transition metal‐catalyzed hydroarylation of alkenes can provide various Markovnikov products, but so‐called anti‐Markovnikov additions to alkenes are rarely reported. Here, a divalent nickel hydride complex catalyzed anti‐Markovnikov reductive cross‐coupling of styrene and aryl iodide has been investigated using density functional theory. The reaction occurs via the regio‐determining hydronickelation, the oxidative addition of the CI bond to Ni(II) center, and the rate‐determining reductive elimination of hydroarylation product. The electronic processes were investigated with a fragment molecular orbital analysis to understand the origin of anti‐Markovnikov selectivity and successive oxidative addition and reductive elimination steps.