Department of Chemistry, University of California, Berkeley, Berkeley, CA, 94720, USA.
Angew Chem Int Ed Engl. 2020 Oct 19;59(43):18898-18919. doi: 10.1002/anie.201915657. Epub 2020 Aug 24.
Transition-metal-mediated cleavage of C-C single bonds can enable entirely new retrosynthetic disconnections in the total synthesis of natural products. Given that C-C bond cleavage inherently alters the carbon framework of a compound, and that, under transition-metal catalysis, the generated organometallic or radical intermediate is primed for further complexity-building reactivity, C-C bond-cleavage events have the potential to drastically and rapidly remodel skeletal frameworks. The recent acceleration of the use of transition-metal-mediated cleavage of C-C single bonds in total synthesis can be ascribed to a communal recognition of this fact. In this Review, we highlight ten selected total syntheses from 2014 to 2019 that illustrate how transition-metal-mediated cleavage of C-C single bonds at either the core or the periphery of synthetic intermediates can streamline synthetic efforts.
过渡金属介导的 C-C 单键断裂可以在天然产物的全合成中实现全新的逆合成切断。由于 C-C 键的断裂本质上改变了化合物的碳骨架，而且在过渡金属催化下，生成的有机金属或自由基中间体为进一步的复杂构建反应做好了准备，因此 C-C 键的断裂有可能急剧而迅速地重塑骨架。最近在全合成中加速使用过渡金属介导的 C-C 单键断裂，可以归因于人们共同认识到了这一事实。在这篇综述中，我们重点介绍了 2014 年至 2019 年的十个选定的全合成，这些全合成说明了如何通过在合成中间体的核心或外围处用过渡金属介导的 C-C 单键断裂来简化合成工作。
