当前位置:
X-MOL 学术
›
J. Am. Chem. Soc.
›
论文详情
Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
Electron-Transfer Photoredox Catalysis: Development of a Tin-Free Reductive Dehalogenation Reaction
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2009-07-01 , DOI: 10.1021/ja9033582
Jagan M. R. Narayanam 1 , Joseph W. Tucker 1 , Corey R. J. Stephenson 1
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2009-07-01 , DOI: 10.1021/ja9033582
Jagan M. R. Narayanam 1 , Joseph W. Tucker 1 , Corey R. J. Stephenson 1
Affiliation
![]() |
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.
中文翻译:
电子转移光氧化还原催化:无锡还原脱卤反应的发展
我们报告了一种操作简单、无锡的还原脱卤系统,该系统利用众所周知的可见光活化光氧化还原催化剂 Ru(bpy)(3)Cl(2) 结合 (i)Pr(2)NEt 和 HCO(2) )H 或 Hantzsch 酯作为氢原子供体。与芳基和乙烯基 CX 键相比,活化的 CX 键可以以良好的收率减少,具有优异的官能团耐受性和化学选择性。所提出的机制涉及催化剂的可见光激发,其被叔胺还原以产生单电子还原剂 Ru(bpy)(3)(+)。随后的单电子转移产生烷基自由基,该自由基通过夺取一个氢原子而猝灭。使用低至 0.05 mol% 的 Ru 催化剂就可以在制备规模上完成还原。
更新日期:2009-07-01
中文翻译:

电子转移光氧化还原催化:无锡还原脱卤反应的发展
我们报告了一种操作简单、无锡的还原脱卤系统,该系统利用众所周知的可见光活化光氧化还原催化剂 Ru(bpy)(3)Cl(2) 结合 (i)Pr(2)NEt 和 HCO(2) )H 或 Hantzsch 酯作为氢原子供体。与芳基和乙烯基 CX 键相比,活化的 CX 键可以以良好的收率减少,具有优异的官能团耐受性和化学选择性。所提出的机制涉及催化剂的可见光激发,其被叔胺还原以产生单电子还原剂 Ru(bpy)(3)(+)。随后的单电子转移产生烷基自由基,该自由基通过夺取一个氢原子而猝灭。使用低至 0.05 mol% 的 Ru 催化剂就可以在制备规模上完成还原。