Direct phosphorylation of benzylic C-H bonds under transition metal-free conditions forming sp 3 C-P bonds.

Direct phosphorylation of benzylic C-H bonds was achieved in a biphasic system under transition metal-free conditions. A selective radical/radical sp 3 C-H/P(O)-H cross coupling was proposed, and various substituted toluenes were applicable. The transformation provided a promising method for constructing sp 3 C-P bonds.