Electron-Transfer Photoredox Catalysis: Development of a Tin-Free Reductive Dehalogenatioin Reaction

被引：816

作者：

Narayanam, Jagan M. R. ^{[1
]}

Tucker, Joseph W. ^{[1
]}

Stephenson, Corey R. J. ^{[1
]}

机构：

[1] Boston Univ, Dept Chem, Boston, MA 02215 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2009年 / 131卷 / 25期

关键词：

PHOTOCHEMISTRY; CYCLOADDITIONS; COMPLEXES; CHEMISTRY; ALKENES; HALIDES; WATER;

D O I：

10.1021/ja9033582

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

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 'Pr2NEt and HCO2H 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 3 degrees 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.

引用

页码：8756 / +

页数：3

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