The trapping of hexacarbonyldicobalt clusters stabilized propargylic cations by nucleophiles (Nicholas reaction) is a powerful tool. The main shortcomings of the reaction are the use of acid media to generate the carbocation and its inestability at temperatures above -40�C.As an alternative we develop a novel gold (I) and silver (I) catalitic version of the process. The reaction proceeds smoothly at room temperature in good to excellent yieds and the process is diastereoselective when a chiral starting material is used.DFT calculations suggest that the reaction mechanism of the process involves trimetallic species wich undergo a type-I metalla-dyatropic rearrangement.

Gold and silver catalyzed Nicholas reaction: An unusual reaction pathway

244th National Meeting (2012)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.