Enantioselective and Divergent Synthesis of Propargylamides and Allenamides from Alkynyl Diazoketones and Anilines via Organocatalytic Wolff Rearrangements

Abstract Chiral allenes and alkynes are privileged scaffolds in natural products and pharmaceuticals. Although significant advances have been achieved in catalytic asymmetric synthesis from diazo compounds, selectively achieving high levels of both enantioselectivity and regioselectivity from the same starting materials remains challenging. Herein, we report a tunable organocatalytic strategy for the divergent synthesis of chiral allenamides and propargylamides via the Wolff rearrangement of alkynyl diazoketones. By modulating chiral bifunctional catalysts and Lewis acid additives, we achieved excellent control over site selectivity and enantioselectivity. The method features a broad substrate scope, scalability, and applications in late-stage modification of complex molecules, providing a versatile route to valuable enantioenriched building blocks.