Catalytic Asymmetric Total Synthesis of (∿-Actinophyllic Acid
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- 作者：Lingchao Cai ; Kui Zhang ; Ohyun Kwon
- 刊名：Journal of the American Chemical Society
- 出版年：2016
- 出版时间：March 16, 2016
- 年：2016
- 卷：138
- 期：10
- 页码：3298-3301
- 全文大小：373K
- ISSN：1520-5126
文摘
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.