Iodine(III) Reagents in Radical Chemistry

5 years ago

Iodine(III) Reagents in Radical Chemistry

Armido Studer, Xi Wang

The chemistry of hypervalent iodine(III) compounds has gained great interest over the past 30 years. Hypervalent iodine(III) compounds show valuable ionic reactivity due to their high electrophilicity but also express radical reactivity as single electron oxidants for carbon and heteroatom radical generation. Looking at ionic chemistry, these iodine(III) reagents can act as electrophiles to efficiently construct C–CF₃, X–CF₃ (X = heteroatom), C–R_f (R_f = perfluoroalkyl), X–R_f, C–N₃, C–CN, S–CN, and C–X bonds. In some cases, a Lewis or a Bronsted acid is necessary to increase their electrophilicity. In these transformations, the iodine(III) compounds react as formal “CF₃⁺”, “R_f⁺”, “N₃⁺”, “Ar⁺”, “CN⁺”, and “X⁺” equivalents. On the other hand, one electron reduction of the I(III) reagents opens the door to the radical world, which is the topic of this Account that focuses on radical reactivity of hypervalent iodine(III) compounds such as the Togni reagent, Zhdankin reagent, diaryliodonium salts, aryliodonium ylides, aryl(cyano)iodonium triflates, and aryl(perfluoroalkyl)iodonium triflates. Radical generation starting with I(III) reagents can also occur via thermal or light mediated homolysis of the weak hypervalent bond in such reagents. This reactivity can be used for alkane C–H functionalization. We will address important pioneering work in the area but will mainly focus on studies that have been conducted by our group over the last 5 years.

Publisher URL: http://dx.doi.org/10.1021/acs.accounts.7b00148

DOI: 10.1021/acs.accounts.7b00148