Mechanism-Driven Development of Group 10 Metal-Catalyzed Decarbonylative Coupling Reactions,Accounts of Chemical Research

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Mechanism-Driven Development of Group 10 Metal-Catalyzed Decarbonylative Coupling Reactions
Accounts of Chemical Research ( IF 16.4 ) Pub Date : 2022-11-16 , DOI: 10.1021/acs.accounts.2c00496
Naish Lalloo ₁ , Conor E Brigham ₁ , Melanie S Sanford ₁

Affiliation

Transition-metal-catalyzed cross-coupling reactions are widely used in both academia and industry for the construction of carbon–carbon and carbon–heteroatom bonds. The vast majority of cross-coupling reactions utilize aryl (pseudo)halides as the electrophilic coupling partner. Carboxylic acid derivatives (RC(O)X) represent a complementary class of electrophiles that can engage in decarbonylative couplings to produce analogous products. This decarbonylative approach offers the advantage that RC(O)X are abundant and inexpensive. In addition, decarbonylative coupling enables both intramolecular (between R and X of the carboxylic acid derivative) as well as intermolecular bond-forming reactions (in which an exogeneous nucleophile is coupled with the R group derived from RC(O)X). In these intermolecular reactions, the X-substituent on the carboxylic acid can be tuned to facilitate both oxidative addition and transmetalation, thus eliminating the need for an exogeneous base. This Account details our group’s development of a diverse variety of base-free decarbonylative coupling reactions catalyzed by group 10 metals. Furthermore, it highlights how catalyst design can be guided by stoichiometric organometallic studies of these systems.

中文翻译：

第10族金属催化脱羰偶联反应的机理驱动发展

过渡金属催化的交叉偶联反应在学术界和工业界广泛用于构建碳-碳和碳-杂原子键。绝大多数交叉偶联反应利用芳基（拟）卤化物作为亲电偶联配偶体。羧酸衍生物 (RC(O)X) 代表一类互补的亲电子试剂，可以参与脱羰基偶联以产生类似的产物。这种脱羰方法的优点是 RC(O)X 丰富且廉价。此外，脱羰偶联可实现分子内（羧酸衍生物的 R 和 X 之间）以及分子间成键反应（其中外源亲核试剂与源自 RC(O)X 的 R 基团偶联）。在这些分子间反应中，可以调整羧酸上的X-取代基以促进氧化加成和金属转移，从而消除对外源碱的需要。本报告详细介绍了我们小组开发的各种由第 10 族金属催化的无碱脱羰偶联反应。此外，它还强调了如何通过这些系统的化学计量有机金属研究来指导催化剂设计。

更新日期：2022-11-16

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