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Synfacts 2025; 21(07): 704
DOI: 10.1055/a-2601-5105
Metals in Synthesis

Photochemical Transfer of C(sp2)–I Bonds to C(sp3)–I Bonds via a Palladium-Catalyzed HAT Reaction

Contributor(s):
Mark Lautens 
,
Andrew G. Durant
Le SauxE, Morandi B *. ETH Zürich, Switzerland
Palladium-Catalyzed Transfer Iodination from Aryl Iodides to Nonactivated C(sp3)–H Bonds.

J. Am. Chem. Soc. 2025;
147: 12956-12961
DOI: 10.1021/jacs.5c02553
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Keywords

palladium - iodide transfer - photochemistry - recyclable

Significance

The Morandi group reports on the transfer iodination of aryl iodide bonds to alkyl iodide bonds. They were able to use palladium/blue light catalysis to generate an aryl radical that undergoes HAT, resulting in an alkyl radical. They showed that this alkyl radical undergoes halogen atom transfer (XAT) from the PdI center to furnish the product and regenerate the catalyst.


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Comment

The selectivity of the hydrogen atom transfer (HAT) event was investigated in detail. It was shown that both steric and electronic effects played a role. In examples with a cyclohexyl core, larger groups disfavored HAT on nearby hydrogens. In examples of linear substrates, electron-withdrawing groups favored HAT away from the electron-withdrawing site, likely due to the electrophilic nature of the radical formed.


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Publication History

Article published online:
23 June 2025

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