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<p>Markovnikov-selective hydroamination of unactivated terminal alkenes has long remained a challenging transformation in C–N bond formation. Fan and co-workers<sup>1</sup> 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.</p> Graphical abstract <p>Metal-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(sp<sup>3</sup>)–N bond formation.</p>

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Phosphine radical cation catalysis for Markovnikov hydroamination of unactivated alkenes

  • 期刊论文

  • 发表日期：

    2026年4月24日

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  • Nirmal Das,
  • Nagaraju Barsu

摘要

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 abstract

Metal-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.