Photoredox-HAT Catalysis for Primary Amine α-C–H Alkylation: Mechanistic Insight with Transient Absorption Spectroscopy

[Image: see text] The synergistic use of (organo)photoredox catalysts with hydrogen-atom transfer (HAT) cocatalysts has emerged as a powerful strategy for innate C(sp(3))–H bond functionalization, particularly for C–H bonds α- to nitrogen. Azide ion (N(3)(–)) was recently identified as an effective HAT catalyst for the challenging α-C–H alkylation of unprotected, primary alkylamines, in combination with dicyanoarene photocatalysts such as 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN). Here, time-resolved transient absorption spectroscopy over sub-picosecond to microsecond timescales provides kinetic and mechanistic details of the photoredox catalytic cycle in acetonitrile solution. Direct observation of the electron transfer from N(3)(–) to photoexcited 4CzIPN reveals the participation of the S(1) excited electronic state of the organic photocatalyst as an electron acceptor, but the N(3)(•) radical product of this reaction is not observed. Instead, both time-resolved infrared and UV–visible spectroscopic measurements implicate rapid association of N(3)(•) with N(3)(–) (a favorable process in acetonitrile) to form the N(6)(•–) radical anion. Electronic structure calculations indicate that N(3)(•) is the active participant in the HAT reaction, suggesting a role for N(6)(•–) as a reservoir that regulates the concentration of N(3)(•).