Iron-Catalyzed <i>Ipso</i>-Nitration ofAryl Borides via Visible-Light-Induced β‑Homolysis

Herein, we reported a practical method to realize <i>ipso</i>-nitration of boronic acids, their pinacol esters, and trifluoroborate salts with alkali metal salt NaNO<sub>3</sub> as a nitrating reagent. A Fe<sup>III</sup>/Fe<sup>IV</sup> catalytic cycle involving an unusual visible-light-induced β-homolysis pathway of the N–O bond in a simple iron complex effectively provides a nitryl radical as the key nitrating species. This protocol bears mild reaction conditions, a broad scope (up to 99% yield), good functional group compatibility, and convenient scale-up synthesis.

Publication Details

Journal
Figshare
Published
2025-02-07
DOI
https://doi.org/10.1021/acscatal.4c07252.s001
Primary Topic
Radical Photochemical Reactions
Type
article
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article

Iron-Catalyzed Ipso-Nitration ofAryl Borides via Visible-Light-Induced β‑Homolysis

Figshare
Radical Photochemical Reactions
article

Iron-Catalyzed Ipso-Nitration ofAryl Borides via Visible-Light-Induced β‑Homolysis

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Abstract

Herein, we reported a practical method to realize <i>ipso</i>-nitration of boronic acids, their pinacol esters, and trifluoroborate salts with alkali metal salt NaNO<sub>3</sub> as a nitrating reagent. A Fe<sup>III</sup>/Fe<sup>IV</sup> catalytic cycle involving an unusual visible-light-induced β-homolysis pathway of the N–O bond in a simple iron complex effectively provides a nitryl radical as the key nitrating species. This protocol bears mild reaction conditions, a broad scope (up to 99% yield), good functional group compatibility, and convenient scale-up synthesis.

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Radical Photochemical Reactions
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Iron-Catalyzed <i>Ipso</i>-Nitration ofAryl Borides via Visible-Light-Induced β‑Homolysis · Figshare (2025) | TGRS Research Map | TGRS