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The Newman–Kwart Rearrangement of O ‐Aryl Thiocarbamates: Substantial Reduction in Reaction Temperatures through Palladium Catalysis
Author(s) -
Harvey Jeremy N.,
Jover Jesús,
LloydJones Guy C.,
Moseley Jonathan D.,
Murray Paul,
Renny Joseph S.
Publication year - 2009
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.200903908
Subject(s) - thiocarbamate , chemistry , catalysis , palladium , thiocarbamates , aryl , intermolecular force , medicinal chemistry , photochemistry , computational chemistry , organic chemistry , molecule , alkyl
Much cooler : The development of a catalyst for the Newman–Kwart rearrangement allows an escape from the harsh thermal conditions of the standard uncatalyzed reaction (see scheme). Mechanistic investigations, employing kinetic, isotopic labelling ( 2 H, 18 O, 34 S) and DFT studies, suggest that the reaction proceeds through a five‐centred Pd–S coordinated oxidative addition, with intermolecular exchange of aryl and thiocarbamate moieties through dimerization of the resting state.