Advancing the Logic of Chemical Synthesis: C-H Activation as Strategic and Tactical Disconnections for C-C Bond Construction

被引:271
作者
Lam, Nelson Y. S. [1 ]
Wu, Kevin [1 ]
Yu, Jin-Quan [1 ]
机构
[1] Scripps Res Inst, Dept Chem, 10550 North Torrey Pines Rd, La Jolla, CA 92037 USA
关键词
catalysis; C− H activation; H functionalization; total synthesis; transition metals; ASYMMETRIC TOTAL-SYNTHESIS; ENANTIOSELECTIVE TOTAL-SYNTHESIS; RH(I)-CATALYZED DIRECT ARYLATION; CROSS-COUPLING REACTIONS; CONCISE TOTAL-SYNTHESIS; BETA-C(SP(3))-H ARYLATION; STEREOCHEMICAL RELAY; STRUCTURAL REVISION; FORMAL SYNTHESIS; DICTYODENDRIN-B;
D O I
10.1002/anie.202011901
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The design of synthetic routes by retrosynthetic logic is decisively influenced by the transformations available. Transition-metal-catalyzed C-H activation has emerged as a powerful strategy for C-C bond formation, with myriad methods developed for diverse substrates and coupling partners. However, its uptake in total synthesis has been tepid, partially due to their apparent synthetic intractability, as well as a lack of comprehensive guidelines for implementation. This Review addresses these issues and offers a guide to identify retrosynthetic opportunities to generate C-C bonds by C-H activation processes. By comparing total syntheses accomplished using traditional approaches and recent C-H activation methods, this Review demonstrates how C-H activation enabled C-C bond construction has led to more efficient retrosynthetic strategies, as well as the execution of previously unattainable tactical maneuvers. Finally, shortcomings of existing processes are highlighted; this Review illustrates how some highlighted total syntheses can be further economized by adopting next-generation ligand-enabled approaches.
引用
收藏
页码:15767 / 15790
页数:24
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