Photocatalytic Selective N -α-C(sp3)–H Alkylation via Net 1,2-Hydrogen Atom Transfer (HAT) of Trifluoroacetamidyl Radicals with Readily Available N–H Trifluoroacetamides

We have developed a novel α-C(sp3)–H alkylation of trifluoroacetamides via a net 1,2-hydrogen atom transfer (HAT) process of trifluoroacetamidyl radicals with readily available N–H trifluoroacetamides. Remarkably, the prevalent well-known 1,5-HAT pathway has been effectively suppressed, enabling the selective formation of 1,2-HAT-derived α-amino radical intermediates. This protocol features a broad substrate scope across a variety of alkenes and trifluoroacetamides, including those derived from bioactive molecules, thereby demonstrating its high synthetic practicality. Preliminary mechanistic experiments support the feasibility of the net 1,2-HAT process of N-centered radicals.