Aryl Sulfonium Salt Electron Donor-Acceptor Complexes for Halogen Atom Transfer: Isocyanides as tuneable coupling partners

The photoactivation of sulfonium salt EDA complexes provides a mild platform for aryl radical-mediated halogen atom transfer activation of a wide range of functionalized alkyl iodides. Using an aryl sulfonium salt with carbonate as an inexpensive donor for EDA complex formation, the general reaction platform has been applied in a divergent, metal-free pho- tochemical approach to nitriles and amides. This divergency was made possible by tuning the isocyanide radical traps. For example, the identification of a readily accessible, bench-stable and crystalline amide containing isocyanide, grants access to nitrile products with complete selectivity.