Iron‐Photocatalyzed Alkene Chloroaminoxylation: A Platform for Orthogonally Activatable Building Blocks

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ABSTRACT We report the development of an iron‐photocatalyzed 1,2‐chloroaminoxylation of alkenes that installs two orthogonal and independently activatable synthetic handles, a chlorine atom and an alkoxyamino group, across a diverse range of alkene substrates. The reaction is driven by iron's ability to generate chlorine radicals via photoinduced chloride‐to‐iron charge transfer, followed by addition across the carbon–carbon double bond and subsequent trapping by TEMPO derivatives. This operationally simple protocol exhibits broad functional group tolerance, exquisite chemo‐ and regioselectivity and efficiently converts a wide range of C═C bonds, such as styrene derivatives, unactivated alkenes, and Michael acceptors, into synthetically valuable chlorooxygenated scaffolds. The resulting products can be engaged with various nucleophiles through distinct modes of reactivity: the TEMPO‐derived alkoxyamino moiety undergoes photoredox activation, while the C–Cl bond participates in nucleophilic substitution. This dual‐reactivity platform enables a programmable incorporation of two different nucleophiles under complementary activation conditions, providing streamlined access to structurally diverse architectures. Comprehensive mechanistic studies, integrating reaction kinetics, UV–vis spectroscopy, high‐resolution mass spectrometry (HRMS), x‐ray crystallographic characterization of key catalytic intermediates, cyclic voltammetry (CV), and chronoamperometry, elucidate the underlying reaction pathway and reveal key features of the iron catalytic cycle.

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