Palladium‐Catalyzed Alkene Thioacylation: A C−S Bond Activation Approach for Accessing Indanone Derivatives

Abstract

A palladium‐catalyzed intramolecular alkene thioacylation reaction initiated by the activation of thioester C(acyl)−S bonds is reported. This approach successfully suppressed decarbonylation and β‐hydrogen elimination with related acyl and alkyl metal thiolate intermediates, providing an efficient and atom‐economical method to access indanone scaffolds. Mechanistic studies provide support for C(acyl)−Pd bond insertion of olefins. The synthetic utility of this protocol is demonstrated by the further conversion of the newly formed methylene sulfide substituent.

Recent Metal-Catalyzed Methods for Thioether Synthesis

“…In 2021, Wu et al disclosed a method for the intramolecular thioacylation featuring the activation of the C(carbonyl)-S bond of thioesters 115 (Scheme 62). 208 The catalyst system consisting of PdCl 2 and ligand dppb (L27) enabled synthesis of a series of indanone derivatives 116 in good yields. DFT calculations indicated the preference for a catalytic cycle based on oxidative addition of Pd into the C-S bond, insertion of the double bond into the Pd-C bond, and final reduction elimination.…”