Tertiary-Alcohol-Directed Functionalization of Remote C(sp3 )-H Bonds by Sequential Hydrogen Atom and Heteroaryl Migrations.

Reported for the first time is a tertiary-alcohol-guided heteroarylation of remote C(sp3 )-H bonds. The mild and direct generation of alkoxyl radicals from alcohols is enabled by visible-light photocatalysis. A remote hydrogen atom and heteroaryl migration sequence are involved in the reaction. Many sensitive groups remain intact in the reaction, thus illustrating wide functional-group compatibility. This protocol provides a practical strategy for the late-stage modification of alkyl ketones.