An Efficient Catalyst Based on Manganese Salen for Hydrosilylation of Carbonyl Compounds
摘要:
A manganese salen complex is shown to be an effective (pre)catalyst in the hydrosilylation of aldehydes and ketones. The present system features an earth-abundant and inexpensive base metal, low catalyst loading, and functional group tolerance. Mechanistic studies suggest that the reaction likely proceeds through a reduced manganese(III) hydride species that undergoes electrophilic attack by the carbonyl substrates.
Scope and Mechanistic Studies of Catalytic Hydrosilylation with a High-Valent Nitridoruthenium(VI)
作者:Srinivas Abbina、Shi Bian、Casey Oian、Guodong Du
DOI:10.1021/cs300848h
日期:2013.4.5
Hydrosilylation catalyzed by a high-valent nitridonithenium(VI) compound, [RuN(saldach)(CH3OH)(+)[ClO4](-) (1, where saldach is the dianion of racemic N,N'-cyclohexan-diyl-bis(salicylideneimine)) is described. Using phenylsilane as reductant, a variety of unsaturated organic substrates, including aldehydes, ketones, and imines, are effectively reduced to alcohols and amines, respectively, accompanied by the redistribution of PhSiH3 at silicon. Mechanistic studies indicate that the catalysis proceeds via silane activation rather than carbonyl activation, and the silane is likely activated via multiple pathways, including a radical-based pathway.