Gold(I)-Catalyzed Enantioselective Carboalkoxylation of Alkynes

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.

本文报道了以阳离子型(DTBM-MeO-Biphep)金(I)配合物为催化剂，实现炔烃的高对映选择性碳烷氧基化反应。该反应可获得收率优良、对映选择性优异的各类光学活性β-烷氧基茚酮衍生物。此外，该合成方法还可拓展应用于3-甲氧基环戊烯酮的对映选择性合成。据推测，该反应经由包含乙烯基金(I)与前手性氧鎓离子片段的中间体发生对映选择性环化过程进行。