Catalytic Asymmetric Total Synthesis of (-)-Actinophyllic Acid.
Catalytic Asymmetric Total Synthesis of (-)-Actinophyllic Acid.
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DOI：
10.1021/jacs.6b00567
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发表时间：
2016-03-16
影响因子：
15
通讯作者：
Kwon O
中科院分区：
文献类型：
--
作者：
Cai L;Zhang K;Kwon O
本发明描述了一种催化不对称全合成（-）-放线菌酸的方法，其关键步骤是手性膦催化的亚胺和丙二烯酸酯之间的[3 + 2]成环反应，以99%的产率和94%ee形成吡咯啉中间体。SmI 2介导的酮和内酯亚基之间的分子内频哪醇偶联，组装（−）-放线菌酸的复杂骨架;以及前所未有的区域选择性脱羟基作用。
Described herein is a catalytic asymmetric total synthesis of (−)-actinophyllic acid, with the key step being a chiral phosphine-catalyzed [3 + 2] annulation between an imine and an allenoate to form a pyrroline intermediate in 99% yield and 94% ee. The synthesis also features CuI-catalyzed coupling between a ketoester and a 2-iodoindole to shape the tetrahydroazocine ring; intramolecular alkylative lactonization; SmI2-mediated intramolecular pinacol coupling between ketone and lactone subunits to assemble the complex skeleton of (−)-actinophyllic acid; and an unprecedented regioselective dehydroxylation.