Catalytic asymmetric allylic C-H activation as a surrogate of the asymmetric Claisen rearrangement.
[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.
Davies
H M
HM
Department of Chemistry, University at Buffalo, State University of New York, Buffalo, New York 14260-3000, USA. hdavies@acsu.buffalo.edu
Ren
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P
Jin
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