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Ruthenium‐Catalyzed para ‐Selective C−H Alkylation of Aniline Derivatives
Author(s) -
Leitch Jamie A.,
McMullin Claire L.,
Paterson Andrew J.,
Mahon Mary F.,
Bhonoah Yunas,
Frost Christopher G.
Publication year - 2017
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.201708961
Subject(s) - ruthenium , metalation , aniline , alkylation , catalysis , chemistry , combinatorial chemistry , regioselectivity , medicinal chemistry , organic chemistry
The para ‐selective C−H alkylation of aniline derivatives furnished with a pyrimidine auxiliary is herein reported. This reaction is proposed to take place via an N−H‐activated cyclometalate formed in situ. Experimental and DFT mechanistic studies elucidate a dual role of the ruthenium catalyst. Here the ruthenium catalyst can undergo cyclometalation by N−H metalation (as opposed to C−H metalation in meta ‐selective processes) and form a redox active ruthenium species, to enable site‐selective radical addition at the para position.