Ogiwara Yohei, Sakai Norio
Department of Pure and Applied Chemistry, Faculty of Science and Technology, Tokyo University of Science, Noda, Chiba, 278-8510, Japan.
Angew Chem Int Ed Engl. 2020 Jan 7;59(2):574-594. doi: 10.1002/anie.201902805. Epub 2019 Oct 31.
In this Review, we summarize the current state of the art in late-transition-metal-catalyzed reactions of acyl fluorides, covering both their synthesis and further transformations. In organic reactions, the relationship between stability and reactivity of the starting substrates is usually characterized by a trade-off. Yet, acyl fluorides display a very good balance between these properties, which is mostly due to their moderate electrophilicity. Thus, acyl fluorides (RCOF) can be used as versatile building blocks in transition-metal-catalyzed reactions, for example, as an "RCO" source in acyl coupling reactions, as an "R" source in decarbonylative coupling reactions, and as an "F" source in fluorination reactions. Starting from the cleavage of the acyl C-F bond in acyl fluorides, various transformations are accessible, including C-C, C-H, C-B, and C-F bond-forming reactions that are catalyzed by transition-metal catalysts that contain the Group 9-11 metals Co, Rh, Ir, Ni, Pd, or Cu.
在本综述中，我们总结了后过渡金属催化的酰氟反应的当前技术水平，涵盖了它们的合成及其进一步转化。在有机反应中，起始底物的稳定性和反应性之间的关系通常表现为一种权衡。然而，酰氟在这些性质之间展现出非常良好的平衡，这主要归因于它们适度的亲电性。因此，酰氟（RCOF）可作为通用的结构单元用于过渡金属催化的反应中，例如，在酰基偶联反应中作为“RCO”源，在脱羰偶联反应中作为“R”源，以及在氟化反应中作为“F”源。从酰氟中酰基C-F键的断裂出发，可以实现各种转化，包括由含有第9-11族金属Co、Rh、Ir、Ni、Pd或Cu的过渡金属催化剂催化的C-C、C-H、C-B和C-F键形成反应。
