Abstract
We report an operationally simple, tin-free reductive dehalogenation system utilizing the well-known visible-light-activated photoredox catalyst Ru(bpy)(3)Cl(2) in combination with (i)Pr(2)NEt and HCO(2)H or Hantzsch ester as the hydrogen atom donor. Activated C-X bonds may be reduced in good yields with excellent functional-group tolerance and chemoselectivity over aryl and vinyl C-X bonds. The proposed mechanism involves visible-light excitation of the catalyst, which is reduced by the tertiary amine to produce the single-electron reducing agent Ru(bpy)(3)(+). A subsequent single-electron transfer generates the alkyl radical, which is quenched by abstraction of a hydrogen atom. Reductions can be accomplished on a preparative scale with as little as 0.05 mol % Ru catalyst.
Keywords
ChemistryChemoselectivityCatalysisPhotoredox catalysisPhotochemistryHalogenationHydrogen atomTinElectron transferAlkylArylHydrogen atom abstractionAmine gas treatingFunctional groupProton-coupled electron transferCombinatorial chemistryHydrogenOrganic chemistryPhotocatalysis
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Publication Info
- Year
- 2009
- Type
- article
- Volume
- 131
- Issue
- 25
- Pages
- 8756-8757
- Citations
- 949
- Access
- Closed
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Cite This
Jagan M. R. Narayanam,
Joseph W. Tucker,
Corey R. J. Stephenson
(2009).
Electron-Transfer Photoredox Catalysis: Development of a Tin-Free Reductive Dehalogenation Reaction.
Journal of the American Chemical Society
, 131
(25)
, 8756-8757.
https://doi.org/10.1021/ja9033582
Identifiers
- DOI
- 10.1021/ja9033582
- PMID
- 19552447