Donor/acceptor-substituted rhodium carbenoids participate on a broad range of synthetically useful transformations. Among these, the vinylcarbenoids are particularly interesting because of their capability of catalyst-controlled vinyl or carbenoid reactivity. These have been employed in C-H functionalization/Cope rearrangement, [2,3]-sigmatropic rearrangement/oxy-Cope rearrangement/ene reaction, cyclopropanation of electron deficient alkenes, and most recently [3+2] cycloaddition with nitrones. Methodology towards the enantioselective reactions of vinylcarbenoids and silyl ketene acetals with Rh<sub>2</sub>(S-DOSP)<sub>4</sub> to generate [3+2] cycloadducts with three new stereogenic centers in high yields is being developed. Complementary methodology employing the same reaction partners with the more bulky triaryl cyclopropane carboxylate Rh catalysts promote vinyl reactivity yielding 1,6-diones with high diastereoselectivity. The substrate scope of reactions of vinylcarbenoids and silyl ketene acetals with a variety of dirhodium catalysts that promote distinct reactivity are described.

Rhodium-catalyst controlled carbenoid and vinylogous reactions of vinyldiazoacetates and silyl ketene acetals

249th National Meeting (2015)

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