Three-Component Friedel-Crafts Transformations: Synthesis ofAlkyl and Alkenyl Trifluoromethyl Sulfides and Alkenyl Iodides

Straightforward and mild hexafluoroisopropanol(HFIP)-mediated, metal-free, three-component Friedel-Craftsapproaches are reported for the synthesis of alkenyl and alkyltrifluoromethyl sulfides from arenes, (PhSO2)2NSCF3, and alkynesor alkenes, respectively. The transformations proceed with highregio- and stereochemical control via the initial formation ofcationic thiirenium and thiiranium intermediates, respectively,followed by Friedel-Crafts reactions with the arene. Amechanistically related three-component synthesis of alkenyl iodides from arenes, alkenes, andN-iodosuccinimide is also reported

Automated summary

Straightforward and mild metal-free three-component Friedel-Crafts approaches using hexafluoroisopropanol (HFIP) as mediator were reported for the synthesis of alkenyl and alkyltrifluoromethyl sulfides from arenes, (PhSO2)2NSCF3, and alkynes or alkenes. The transformations showed high regio- and stereochemical control through the formation of cationic thiirenium and thiiranium intermediates followed by Friedel-Crafts reactions with arenes. A mechanistically related three-component synthesis of alkenyl iodides from arenes, alkenes, and N-iodosuccinimide was also described.