210. Enantioselective C−C Bond Formation by Rhodium-Catalyzed Tandem Ylide Formation/[2,3]-Sigmatropic Rearrangement between Donor/Acceptor Carbenoids and Allylic Alcohols

Authors: Zhanjie Li and Huw M. L. Davies

J. Am. Chem. Soc.,

2010, 132 (1), 396–401


The rhodium-catalyzed reaction of racemic allyl alcohols with methyl phenyldiazoacetate or methyl styryldiazoacetate results in a two-step process, an initial oxonium ylide formation followed by a [2,3]-sigmatropic rearrangement. This process competes favorably with the more conventional O−H insertion chemistry as long as donor/acceptor carbenoids and highly substituted allyl alcohols are used as substrates. When the reactions are catalyzed by Rh2(S-DOSP)4, tertiary α-hydroxycarboxylate derivatives with two adjacent quaternary centers are produced with high enantioselectivity (85−98% ee).

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