Disproportionation of acyclic ketones to carboxylate ions and ethers: a poisoning reaction on the way to the chemoselective reduction of α,β-unsaturated ketones to allylic alcohols via hydrogen-transfer catalysed by a nonclassical ruthenium(II) trihydride

Abstract

The nonclassical trihydride [Ru(tdpep)(H)(H₂)]BPh₄1 catalyses under mild conditions the chemoselective reduction of α,β-unsaturated ketones to allylic alcohols via hydrogen-transfer [tdpep = P(CH₂CH₂PPh₂)₃]; compound 1 reacts with acyclic ketones (or aldehydes) yielding stable η²-carboxylate complexes of general formula [Ru(tdpep)(O₂CR)]BPh₄, and ethers (or ethers plus esters).