Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH5304, CH-1015 Lausanne, Switzerland.
Chem Soc Rev. 2018 Oct 29;47(21):7882-7898. doi: 10.1039/c8cs00454d.
From tryptamine and secologanine, nature generates monoterpene indole alkaloids with an unprecedented level of skeletal diversity through a 'couple-divert' sequence. Intrigued by this biosynthetic machinery, new strategies and tactics to access skeletally distinct natural products are continuously emerging. In this Tutorial Review, we'll present a simplified view of nature's logic for biosynthesis and the representative strategies and tactics developed for the divergent total synthesis of monoterpene indole alkaloids. Our group has been developing a 'couple-divert' approach with the strategic use of cycloalkene as a pluripotent motif in the synthetic design and has developed an integrated oxidation/reduction/cyclization (iORC) sequence for transforming functionalized cycloalkenes, easily available by a variety of cross-coupling reactions, to skeletally diverse natural products. The integration of controlled regio-, chemo- and stereo-selective cyclization and heteroannulation reactions into these domino sequences will be highlighted.
从色胺和赛洛拉宁出发，自然界通过“偶联-转换”序列生成了具有空前结构多样性的单萜吲哚生物碱。受这种生物合成机制的启发，人们不断开发出获取具有独特骨架的天然产物的新策略和战术。在本综述中，我们将呈现出一个简化的自然界生物合成逻辑视图，以及为单萜吲哚生物碱的发散全合成开发的代表性策略和战术。我们小组一直在开发一种“偶联-转换”方法，在合成设计中战略性地使用环烯烃作为多能基元，并开发了一个集成的氧化/还原/环化（iORC）序列，用于将通过各种交叉偶联反应容易获得的功能化环烯烃转化为具有独特骨架的天然产物。这些串联反应序列中区域、化学和立体选择性环化和杂原子环合反应的可控性将被重点强调。
