Hypervalent Iodine-based Trifluoromethylating Agents Made in Switzerland

Abstract

This account aims at providing a general overview over studies carried out in our group on 3,3-dimethyl-1-(trifluoromethyl)-3H-1?3,2-benziodaoxole (1) and 1-(trifluoromethyl)-3H-1?3,2-benziodaoxol-3-one (2). While the first part deals with the syntheses of these increasingly popular reagents, the second part provides in-depth analyses of solid state structures of different derivatives. By means of bond-length derived parameters p changes in the hypervalent bond resulting from backbone modifications could be classified. Furthermore, it is showcased that the parameter p also correlates to solution phase reactivities. Lastly, diverse strategies directed towards the activation of the reagents are exemplified based on selected applications of 1 and 2.

Keywords

• Electrophilic trifluoromethylation
• Hypervalent iodine
• Structure–reactivity relationship