Catalytic Asymmetric Allylic C−H Activation as a Surrogate of the Asymmetric Claisen Rearrangement

Abstract

[reaction: see text]. Tetrakis[N-[4-dodecylphenyl)sulfonyl]-(S)-prolinato]-dirhodium [Rh2(S-DOSP)4] catalyzed decomposition of methyl aryldiazoacetates in the presence of alkenes results in allylic C-H activation by means of a rhodium-carbene induced C-H insertion. The resulting gamma,delta-unsaturated esters are equivalent to products that would be traditionally obtained from an asymmetric Claisen rearrangement. Highly regio- and enantioselective C-H insertions can be achieved, and in certain cases, good diastereocontrol is also possible.