Markovnikov-selective hydroamination of unactivated terminal alkenes has long remained a challenging transformation in C-N bond formation. Fan and co-workers1 addressed this using a metal-free phosphine photoredox system that operates via an unprecedented phosphine radical cation (P(IV)) mechanism, enabling alkene activation toward azole addition. This work highlights a powerful new strategy for C(sp3)-N bond construction beyond traditional transition-metal catalysis.Graphical abstractMetal-free phosphine photoredox catalysis enables Markovnikov-selective hydroamination of unactivated terminalalkenes via a novel phosphine radical cation mechanism, off ering a new strategy for C(sp3)-N bond formation.

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