Rhodium-Catalyzed Regio- and Enantioselective Allylic Sulfonylation from Sulfonyl Hydrazides.

A highly regio- and enantioselective allylic sulfonylation has been developed with rhodium and bisoxazolinephosphine (NPN*) ligands from racemic branched allylic carbonates and readily available sulfonyl hydrazides under neutral conditions. Branch-selective allylic sulfones with a >20:1 branch:linear ratio and >99% could be synthesized in ≤96% yield. Both and linear allylic carbonates could also be converted into the same chiral branched allylic sulfones with high regio- and enantioselectivities.