Selectfluor® Radical Dication (TEDA2+.) – A Versatile Species in Modern Synthetic Organic Chemistry

: In radical processes involving Selectfluor®, TEDA2+. (N‐(chloromethyl)triethylenediamine) is often generated after an electron or fluorine transfer step. This is a highly reactive species that displays different and unique reactivity when compared to Selectfluor®: It can act as a hydrogen atom transfer (HAT), halogen atom transfer (XAT), or aminating reagent, as well as a powerful single electron oxidant. Despite this versatility, the use of TEDA2+. in synthetic processes remains highly underexplored. This minireview, which covers recent applications of TEDA2+. to promote a wide range of C‐heteroatom and C−C bond formations, aims to highlight the potential of this interesting species in organic chemistry. Particular attention is paid to mechanistic aspects involving how TEDA2+. is generated and the different reactivity patterns that it can display. Photochemistry: This review aims to highlight recent progress on the applications of Selectfluor®‐derived radical dication TEDA2+. in synthetic organic chemistry. This species offers distinct and diverse reactivity patterns that can be exploited to promote the formation of a wide range of C–heteroatom and C−C bonds via radical processes.