Asymmetric Construction of Six-Membered Rings by Cyclization of Allenes with Dinuclear Gold Catalysis.

Abstract

A simple and efficient method for the synthesis of 1,4-dihydroarenes by gold-catalyzed 6-endo cyclization of benzylic allenes has been developed. Furthermore, asymmetric hydroarylation of enantioenriched allenes has been realized to offer a practical and convergent approach to aromatic ring-fused six-membered cycles containing a chiral stereocenter such as 1,4-dihydronaphthalenes, 1,4-dihydrodibenzo[b,d]thiophenes, and 4,7-dihydrobenzo[b]thiophenes by applying dinuclear [(dppm)Au2 Cl2 ] [dppm=methylenebis(diphenylphosphane)] combined with AgOTf as the catalyst to ensure the high efficiency of chirality transfer. ESI-MS has been applied to characterize some of the key reactive dinuclear gold intermediates successfully.