Topczewski Joseph J, Sanford Melanie S
Department of Chemistry, University of Michigan, Ann Arbor, MI, 48108, USA.
Chem Sci. 2015 Jan;6(1):70-76. doi: 10.1039/C4SC02591A.
The direct functionalization of carbon-hydrogen (C-H) bonds has emerged as a versatile strategy for the synthesis and derivatization of organic molecules. Among the methods for C-H bond activation, catalytic processes that utilize a Pd/Pd redox cycle are increasingly common. The C-H activation step in most of these catalytic cycles is thought to occur at a Pd centre. However, a number of recent reports have suggested the feasibility of C-H cleavage occurring at Pd complexes. Importantly, these latter processes often result in complementary reactivity and selectivity relative to analogous transformations at Pd. This Mini Review highlights proposed examples of C-H activation at Pd centres. Applications of this transformation in catalysis as well as mechanistic details obtained from stoichiometric model studies are discussed. Furthermore, challenges and future perspectives for the field are reviewed.
碳氢键(C-H)的直接官能团化已成为有机分子合成和衍生化的一种通用策略。在碳氢键活化方法中,利用钯/钯氧化还原循环的催化过程越来越普遍。大多数这些催化循环中的碳氢键活化步骤被认为发生在钯中心。然而,最近的一些报道表明碳氢键在钯配合物处发生裂解是可行的。重要的是,相对于钯上的类似转化,这些后续过程通常会产生互补的反应性和选择性。本综述重点介绍了在钯中心进行碳氢键活化的实例。讨论了这种转化在催化中的应用以及从化学计量模型研究中获得的机理细节。此外,还综述了该领域的挑战和未来展望。