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Full Selectivity Control in Cobalt(III)‐Catalyzed C−H Alkylations by Switching of the C−H Activation Mechanism
Author(s) -
Zell Daniel,
Bursch Markus,
Müller Valentin,
Grimme Stefan,
Ackermann Lutz
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201704196
Subject(s) - chemistry , steric effects , electrophile , ligand (biochemistry) , selectivity , cobalt , catalysis , alkylation , stereochemistry , combinatorial chemistry , electrophilic substitution , mechanism (biology) , medicinal chemistry , organic chemistry , receptor , biochemistry , philosophy , epistemology
Abstract Selectivity control in hydroarylation‐based C−H alkylation has been dominated by steric interactions. A conceptually distinct strategy that exploits the programmed switch in the C−H activation mechanism by means of cobalt catalysis is presented, which sets the stage for convenient C−H alkylations with unactivated alkenes. Detailed mechanistic studies provide compelling evidence for a programmable switch in the C−H activation mechanism from a linear‐selective ligand‐to‐ligand hydrogen transfer to a branched‐selective base‐assisted internal electrophilic‐type substitution.