Rhodium(II)-Catalyzed Highly Selective 1,3-Insertion Reactions Using -Sulfonyl-1,2,3-Triazoles with Heteroaryl Ethers or Heteroaryl Alcohols.

The transformation of -sulfonyl-1,2,3-triazoles insertion/rearrangement is achieved using 2-hydroxybenzimidazole or 2-alkoxybenzothiazole over 3 mol % Rh(Oct) for the synthesis of α-((1-benzo[]imidazol-2-yl)amino) ketones or ()-2-alkoxy-2-phenylethenamines. This regio- and stereoselective reaction proceeds under mild conditions, is tolerant of functional groups, and has a broad substrate scope. Notably, while the general rhodium-catalyzed reaction involves sigmatropic rearrangement from an allyl vinyl ether, the present synthetic methodology prevents rearrangement owing to the benzimidazole group, allowing access to ()-olefins.