NIMBE, CEA, CNRS, Université Paris-Saclay, Gif-sur-Yvette, France.
Angew Chem Int Ed Engl. 2016 Nov 2;55(45):14096-14100. doi: 10.1002/anie.201607201. Epub 2016 Oct 10.
Silyl formates are investigated for the first time as surrogates of hydrosilanes. In the presence of a well-defined ruthenium catalyst, these reagents are shown to promote the chemoselective reduction of a variety of aldehydes by transfer hydrosilylation. Mechanistic investigations have shown that genuine hydrosilane species are avoided during catalysis. The mechanism involves a sequence of decarboxylation/insertion/transmetallation steps.
首次研究了硅基甲酸酯作为硅烷的替代物。在确定的钌催化剂的存在下,这些试剂被证明通过转移氢化硅烷化促进了各种醛的化学选择性还原。机理研究表明,在催化过程中避免了真正的硅烷物种。该机理涉及一系列脱羧/插入/转金属化步骤。