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Synthesis of 2-Hydroxymethyl Ketones by Ruthenium Hydride-Catalyzed Cross-Coupling Reaction of α,β-Unsaturated Aldehydes with Primary Alcohols

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journal contribution
posted on 01.01.2010, 00:00 by Aurélien Denichoux, Takahide Fukuyama, Takashi Doi, Jiro Horiguchi, Ilhyong Ryu
The cross-coupling reaction of α,β-unsaturated aldehydes with primary alcohols to give 2-hydroxymethyl ketones was achieved using RuHCl(CO)(PPh3)3 as a catalyst. This atom-economical reaction is likely to proceed via the hydroruthenation of α,β-unsaturated aldehydes followed by an aldol reaction of the resultant enolates with aldehydes to give α-formylated ketones, which undergo transfer hydrogenation with primary alcohols leading to α-hydroxymethyl ketones. The reduction step can generate aldehydes, participating in the next catalytic cycle.