Free-Radical-Promoted Site-Selective C–H Silylation of Arenes by Using Hydrosilanes

A free-radical-promoted aryl/heteroaryl C–H silylation using hydrosilane was developed. This cross-dehydrogenative silylation enables both electron-rich and electron-poor aromatics to afford the desired arylsilanes in unique selectivity. A “para-selectivity” was observed by examination of over 54 examples. This exceptional orientation is quite different from that in Friedel–Crafts C–H silylation or transition-metal-catalyzed dehydrogenative silylation.