1.13 Intramolecular Hydrogen-Atom Transfer

Recent advances in intramolecular hydrogen-atom transfer (HAT) have demonstrated significant utility in C—H functionalization through highly reactive open-shell intermediates. The intramolecular transposition of radical reactivity from select functional groups to generate more stable carbon-centered radicals often proceeds with high regioselectivity, providing novel bond disconnections at otherwise inert and largely indistinguishable positions. This chapter explores the functional groups capable of intramolecular HAT to generate remote radicals and the transformations currently available to the synthetic chemist.