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Hydrogen: a good partner for rhodium‐catalyzed hydrosilylation
Author(s) -
Balan Cédric,
Pop Roxana,
Comte Virginie,
Poinsot Didier,
RatovelomananaVidal Virginie,
Gendre Pierre Le
Publication year - 2014
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.3156
Subject(s) - hydrosilylation , chemistry , catalysis , rhodium , hydrogen , diethyl ether , stoichiometry , ether , organic chemistry , toluene , solvent , medicinal chemistry
The influence of hydrogen pressure on the hydrosilylation of ketones catalyzed by [(( S )‐SYNPHOS)Rh(nbd)]OTf has been studied. We have notably demonstrated that hydrogen significantly affected the outcome of the reaction while not being consumed as stoichiometric reducing agent. In THF, diethyl ether or toluene, the hydrogen pressure exceedingly accelerated the hydrosilylation reaction and preserved or even improved the enantioselectivity of the process. In CH 2 Cl 2 , the rhodium catalyst also showed generally higher catalytic activity under hydrogen pressure. Most serendipitously, several ketones were found to give products of absolute opposite configuration upon performing the hydrosilylation under argon atmosphere or under hydrogen pressure. Copyright © 2014 John Wiley & Sons, Ltd.