Open AccessReduction of Carboxylic Acids to Alcohols via Manganese(I) Catalyzed Hydrosilylation
Author(s) -
Emanuele Antico,
Peter Schlichter,
Christophe Werlé,
Walter Leitner
Publication year - 2021
Publication title -
jacs au
Language(s) - English
Resource type - Journals
ISSN - 2691-3704
DOI - 10.1021/jacsau.1c00140
Subject(s) - hydrosilylation , catalysis , manganese , silylation , silane , chemistry , dissociation (chemistry) , metal , carboxylic acid , reducing agent , silanes , ligand (biochemistry) , combinatorial chemistry , organic chemistry , receptor , biochemistry
The reduction of carboxylic acids to the respective alcohols, in mild conditions, was achieved using [MnBr(CO) 5 ] as the catalyst and bench stable PhSiH 3 as the reducing agent. It was shown that the reaction with the earth-abundant metal catalyst could be performed either with a catalyst loading as low as 0.5 mol %, rare with the use of [MnBr(CO) 5 ], or on a gram scale employing only 1.5 equiv of PhSiH 3 , the lowest amount of silane reported to date for this transformation. Kinetic data and control experiments have provided initial insight into the mechanism of the catalytic process, suggesting that it proceeds via the formation of silyl ester intermediates and ligand dissociation to generate a coordinatively unsaturated Mn(I) complex as the active species.