Unlocking the Potential of β-Fragmentation of Aminophosphoranyl Radicals for Sulfonyl Radical Reactions.

Exploiting β-scission in aminophosphoranyl radicals for radical-mediated transformations has been a longstanding challenge. In this study, we investigated the untapped potential of β-fragmentation in aminophosphoranyl radicals by leveraging the unique properties of the P-N bond and the substituents of P(III) reagents. Our approach carefully considers factors such as cone angle and electronic properties of phosphine and employs density functional theory (DFT) calculations to probe structural and molecular orbital influence. We successfully induced β-fragmentation through N-S bond cleavage of aminophosphoranyl radicals under visible light and mild conditions, generating a range of sulfonyl radicals derived from pyridinium salts via the photochemical activity of electron donor-acceptor (EDA) complexes. This innovative synthetic strategy exhibits broad applicability, including late-stage functionalization, and paves the way for valuable sulfonyl radical-mediated reactions, such as alkene hydrosulfonylation, difunctionalization, and pyridylic C-H sulfonylation.