Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures, Collaborative Innovation Center of Chemistry for Life Sciences, Nanjing University, Nanjing, 210093, China.
Angew Chem Int Ed Engl. 2017 May 2;56(19):5222-5226. doi: 10.1002/anie.201700320. Epub 2017 Apr 5.
A relay formalism is proposed herein for categorizing the interplay among reactants, target product, and catalytic center in transition-metal catalysis, an important factor that can dictate overall catalysis viability and efficiency. In this formalism, transition-metal catalysis can proceed by dissociative relay, associative covalent relay, and associative dative relay modes. An intriguing associative covalent relay process operates in rhodium(III)-catalyzed oxadiazolone-directed alkenyl C-H coupling with alkynes and allows efficient access to primary pyridinylamines. Although the primary pyridinylamine synthesis mechanism is posteriori rationalized, the relay formalism formulated herein can provide an important mechanistic conceptual framework for future catalyst design and reaction development.
本文提出了一种中继形式论，用于分类过渡金属催化中反应物、目标产物和催化中心之间的相互作用，这是决定整体催化可行性和效率的重要因素。在这种形式论中，过渡金属催化可以通过解离中继、缔合共价中继和缔合配位中继模式进行。在铑(III)催化的恶二唑酮导向的烯基 C-H 与炔烃的偶联中，存在一种有趣的缔合共价中继过程，可有效合成仲吡啶基胺。虽然仲吡啶基胺的合成机制是在后验上合理化的，但本文提出的中继形式论可以为未来的催化剂设计和反应开发提供一个重要的机制概念框架。
