Difunctionalization of Styrenes with Perfluoroalkyl and tert‐Butylperoxy Radicals: Room Temperature Synthesis of (1‐(tert‐Butylperoxy)‐2‐perfluoroalkyl)‐ethylbenzene.

A novel strategy for the difunctionalization of styrenes was developed. This synthesis includes the use of electrophilic perfluoroalkyl and tert-butylperoxy radicals and produces (1-(tert-butylperoxy)-2-perfluoroalkyl)ethylbenzene at room temperature, which has been traditionally difficult to synthesize. With at least four radical species included in the transformation, its high chemoselectivity was extraordinary; the results were further elucidated using computational studies. The methodology also holds a good potential for application as a result of its mild reaction conditions, ease of further modification, and insensitivity to moisture and air.