A highly enantioselective carboalkoxylation of alkynes catalyzed by cationic (DTBM-MeO-Biphep)gold(I) complexes is reported. Various optically active β-alkoxyindanone derivatives were obtained in good yields with high enantioselectivities. Furthermore, this methodology was extended to the enantioselective synthesis of 3-methoxycyclopentenones. The reaction is proposed to proceed through an enantioselective cyclization of intermediates containing vinylgold(I) and prochiral oxocarbenium moieties.
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