A gold-catalysed enantioselective Cope rearrangement of achiral 1,5-dienes

Since the discovery of the Cope rearrangement in the 1940s, no asymmetric variant of the rearrangement of achiral 1,5-dienes has emerged, despite the successes that have been achieved with its heteroatom variants (Claisen, aza-Cope, etc.). This article reports the first example of an enantioselective Cope reaction that starts from an achiral diene. The new gold(I) catalyst derived from double Cl(−)-abstraction of ((S)-3,5-xylyl-PHANEPHOS(AuCl)(2)), has been developed for the sigmatropic rearrangement of alkenyl-methylenecyclopropanes. The reaction proceeds at low temperature and the synthetically useful vinylcyclopropane products are obtained in high yield and enantioselectivity. Density functional theory calculations predict that: (1) the reaction proceeds via a cyclic carbenium ion intermediate, (2) the relief of strain in the methylenecyclopropane moiety provides the thermodynamic driving force for the rearrangement and (3) metal complexation of the transition-state structure lowers the rearrangement barriers

Exceptionally fast carbon–carbon bond reductive elimination from gold(III)

Reductive elimination of carbon-carbon (C-C) bonds occurs in numerous metal-catalyzed reactions. This process is well documented for a variety of transition metal complexes. However, C-C bond reductive elimination from a limited number of Au(III) complexes has been shown to be a slow and prohibitive process, generally requiring elevated temperature. Herein, we show that oxidation of a series of mono- and bimetallic Au(I) aryl complexes at low temperature generates observable Au(III) and Au(II) intermediates. We also show that aryl-aryl bond reductive elimination from these oxidized species is not only among the fastest observed for any transition metal, but is also mechanistically distinct from previously studied alkyl-alkyl and aryl-alkyl reductive eliminations from Au(III)