Asymmetric Hydrative Aldol Reaction (HAR) via Vinyl‐Gold Promoted Intermolecular Ynamide Addition to Aldehydes.

Herein, we reported an intermolecular asymmetric hydrative aldol reaction through vinyl‐gold intermediate under ambient conditions. This tandem alkyne hydration and sequential nucleophilic addition afforded a "base‐free" approach to β‐hydroxy amides with high efficiency (up to 95 % yields, >50 examples). Vinyl gold intermediate was applied as reactive nucleophile and Fe(acac)3 was used as the critical co‐catalyst to prevent undesired protodeauration, allowing this transformation to proceed under mild conditions with good functional group tolerance and excellent stereoselectivity (>20 : 1 d.r. and up to 99 % ee). [ABSTRACT FROM AUTHOR]