Catalytic (4+2) Annulation via Regio‐ and Enantioselective Interception of in‐situ Generated Alkylgold Intermediate

A regio‐ and stereoselective stepwise (4+2) annulation of N‐propargylamides and α,β‐unsaturated imines/ketones has been accomplished with synergetic catalysis by a combination of a gold‐complex and a chiral quinine‐derived squaramide (QN‐SQA), leading to highly functionalized chiral tetrahydropyridines/dihydropyrans in good to high yields with generally excellent enantioselectivity. Mechanistic studies and DFT calculations indicate that the in‐situ formed alkylgold species is the key intermediate in this transformation, and the amide group served as a traceless directing group in this highly selective transformation. This method complements the enantioselective (4+2) annulation of allene reagents, providing the formal internal C‐C π‐bond cycloaddition products, which is challenging and remains elusive.