Mn(I)-Catalyzed Carbon-Skeleton Rearrangement of Tertiary Alcohol-Based Aldol Reaction with Aldehydes.

A Mn-catalyzed ligand-directed Csp3-Csp2 coupling of tertiary allylic alcohols with arylaldehydes has been developed. The method provides an efficient approach to access 1,5-diarylpent-1-en-3-ones via carbon-skeleton rearrangement-based aldol reaction.

Rhodium(III)-Catalyzed Oxidative 1,3-Aryl Migration of α-Aryl Allylic Alcohols.

A Rh(III)-catalyzed oxidative 1,3-aryl migration of α-arylallylic alcohols via Csp2-Csp3 σ bond activation has been developed. This method provides an efficient strategy to allow for allylic alcohol-based skeleton rearrangement, in which various secondary and tertiary α-arylallylic alcohols are rapidly converted to ß-aryl-α, ß-unsaturated ketones and aldehydes.