Kawamura Shintaro, Sodeoka Mikiko
Catalysis and Integrated Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama, 351-0198, Japan.
Synthetic Organic Chemistry Laboratory, RIKEN Cluster for Pioneering Research, 2-1 Hirosawa, Wako, Saitama, 351-0198, Japan.
Chem Rec. 2023 Sep;23(9):e202300202. doi: 10.1002/tcr.202300202. Epub 2023 Jul 31.
The demand for practical methods for the synthesis of novel fluoroalkyl molecules is increasing owing to their diverse applications. Our group has achieved efficient difunctionalizing fluoroalkylations of alkenes using fluorinated carboxylic anhydrides as user-friendly fluoroalkyl sources. Fluorinated diacyl peroxide, prepared in situ from carboxylic anhydrides, enables the development of novel reactions when used as a radical fluoroalkylating reagent. In this account, we aim to provide an in-depth understanding of the structure, bonding, and reactivity of fluorinated diacyl peroxides and radicals as well as their control in fluoroalkylation reactions. In the first part of this account, the physical properties and reactivity of diacyl peroxides and fluoroalkyl radicals are described. In the subsequent part, we categorize the reactions into copper-catalyzed and metal-free methods utilizing the oxidizing properties of fluorinated diacyl peroxides. We also outline examples and mechanisms.
由于新型氟代烷基分子的应用广泛，对其合成实用方法的需求日益增长。我们团队已利用氟化羧酸酐作为便捷的氟代烷基源，实现了烯烃的高效双官能化氟代烷基化反应。由羧酸酐原位制备的氟化二酰基过氧化物，用作自由基氟代烷基化试剂时能够开发新型反应。在本综述中，我们旨在深入了解氟化二酰基过氧化物和自由基的结构、键合及反应活性，以及它们在氟代烷基化反应中的控制方法。在本综述的第一部分，描述了二酰基过氧化物和氟代烷基自由基的物理性质及反应活性。在随后部分，我们利用氟化二酰基过氧化物的氧化性质将反应分类为铜催化法和无金属法。我们还概述了实例及反应机理。
