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Diverting Hydrogenations with Wilkinson's Catalyst towards Highly Reactive Rhodium(I) Species
Author(s) -
PereaBuceta Jesus E.,
Fernández Israel,
Heikkinen Sami,
Axenov Kirill,
King Alistair W. T.,
Niemi Teemu,
Nieger Martin,
Leskelä Markku,
Repo Timo
Publication year - 2015
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.201506216
Subject(s) - rhodium , catalysis , chemistry , oxidative addition , reactive intermediate , reductive elimination , hydrogen molecule , hydrogen , organic chemistry , medicinal chemistry , combinatorial chemistry
Abstract The addition of Barton's base has a dramatic effect on the classic rhodium(III)‐mediated hydrogenations promoted by Wilkinson′s catalyst. Following the initial oxidative addition, a barrierless reductive elimination of HCl from the traditional rhodium(III) intermediates instantly produces a rhodium(I) monohydride species, which is remarkably reactive in the hydrogenation of several internal alkynes and functionalized trisubstituted alkenes. The direct formation of this species is unprecedented upon addition of molecular hydrogen and its catalytic potential has been hitherto barely explored.