Matsumoto Akira, Lee Hyo-Jun, Maruoka Keiji
Graduate School of Pharmaceutical Sciences, Kyoto University Sakyo, Kyoto, 606-8501, Japan.
Department of Chemistry, Kunsan National University, Gunsan, 54150, Republic of Korea.
Chem Rec. 2020 Nov 19. doi: 10.1002/tcr.202000132.
In this account, we describe our recent developments on the four-types of hypervalent iodine(III)-mediated radical reactions in organic synthesis. Firstly, the activation of aldehydic C-H bonds can be successfully effected with hypervalent iodine(III) reagents, thereby allowing the synthesis of various ketones with high efficiency. Secondly, the site-selective oxidation of unactivated C(sp )-H bonds of hydrocarbon substrates was realized with designer hypervalent iodine(III) reagents. Thirdly, various perfluoroalkyl and α-aminoalkyl radicals can be generated from sodium perfluoroalkanesulfinates and sodium α-aminoalkanesulfinates, respectively, under the influence of hypervalent iodine(III) reagents. Finally, the efficient generation of difluoromethyl radical from hypervalent difluoroacetoxyliodine(III) reagent was realized by photolysis. These four different strategies are illustrated by using various selective radical approaches.
在本报告中，我们描述了我们在有机合成中四类型高价碘（III）介导的自由基反应方面的最新进展。首先，高价碘（III）试剂能够成功实现醛基C-H键的活化，从而高效地合成各种酮。其次，通过设计的高价碘（III）试剂实现了烃类底物未活化C(sp) -H键的位点选择性氧化。第三，在高价碘（III）试剂的作用下，全氟烷基亚磺酸钠和α-氨基烷基亚磺酸钠分别可以生成各种全氟烷基和α-氨基烷基自由基。最后，通过光解实现了由高价二氟乙酰氧基碘（III）试剂高效生成二氟甲基自由基。这四种不同的策略通过各种选择性自由基方法进行了说明。
