分子内氧化还原-曼尼希反应：便捷合成四氢原小檗碱核心结构
Intramolecular Redox-Mannich Reactions: Facile Access to the Tetrahydroprotoberberine Core.
作者信息
Ma Longle, Seidel Daniel
机构信息
Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, Piscataway, NJ 08854 (USA) http://seidel-group.com.
出版信息
Chemistry. 2015 Sep 7;21(37):12908-13. doi: 10.1002/chem.201501667. Epub 2015 Jul 28.
Abstract
Cyclic amines such as pyrrolidine undergo redox-annulations with 2-formylaryl malonates. Concurrent oxidative amine α-CH bond functionalization and reductive N-alkylation render this transformation redox-neutral. This redox-Mannich process provides regioisomers of classic Reinhoudt reaction products as an entry to the tetrahydroprotoberberine core, enabling the synthesis of (±)-thalictricavine and its epimer. An unusually mild amine-promoted dealkoxycarbonylation was discovered in the course of these studies.
摘要
诸如吡咯烷之类的环状胺与2-甲酰基芳基丙二酸酯发生氧化还原环化反应。同时进行的胺α-C-H键氧化官能团化和还原N-烷基化使该转化反应呈氧化还原中性。这种氧化还原曼尼希反应过程提供了经典莱茵霍德反应产物的区域异构体，作为进入四氢原小檗碱核心结构的途径，从而能够合成（±）-唐松草卡维因及其差向异构体。在这些研究过程中发现了一种异常温和的胺促进的脱烷氧羰基化反应。
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