Gold-Catalyzed Arylative Cope Rearrangement.

Cope rearrangements have garnered significant attention owing to their ability to undergo structural reorganization in stereoselective manner. While substantial advances have been achieved over decades, these rearrangements remained applicable exclusively to parent 1,5-hexadienes. Herein, we disclose the gold-catalyzed arylative Cope rearrangement of 1,6-heptadienes via a cyclization-induced [3,3]-rearrangement employing ligand-enabled gold redox catalysis. Detailed mechanistic investigations including several control experiments, cross-over experiment, HRMS analysis, 31P NMR and DFT studies have been performed to underpin the mechanism.

Enantioselective merged gold/organocatalysis.

Gold complexes, because of their unique carbophilic nature, have evolved as efficient catalysts for catalyzing various functionalization reactions of C-C multiple bonds. However, the realization of enantioselective transformations via gold catalysis remains challenging due to the geometrical constraints and coordination behaviors of gold complexes. In this context, merged gold/organocatalysis has emerged as one of the intriguing strategies to achieve enantioselective transformations which could not be possible by using a single catalytic system. Historically, in 2009, this field started with the merging of gold with axially chiral Brønsted acids and chiral amines to achieve enantioselective transformations. Since then, based on the unique reactivity profiles offered by each catalyst, several reports utilizing gold in conjunction with various chiral organocatalysts such as amines, Brønsted acids, N-heterocyclic carbenes, hydrogen-bonding and phosphine catalysts have been documented in the literature. This article demonstrates an up-to-date development in this field, especially focusing on the mechanistic interplay of gold catalysts with chiral organocatalysts.