Development of New Radical-mediated Selective Reactions Promoted by Hypervalent Iodine(III) Reagents

Abstract

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(sp³ )-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.

Keywords: acyl radical; hypervalent iodine; perfluoroalkyl radical; radical reaction; site-selective oxidation.