Zuo Zhiwei, Ahneman Derek T, Chu Lingling, Terrett Jack A, Doyle Abigail G, MacMillan David W C
Merck Center for Catalysis at Princeton University, Princeton, NJ 08544, USA.
Science. 2014 Jul 25;345(6195):437-40. doi: 10.1126/science.1255525. Epub 2014 Jun 5.
Over the past 40 years, transition metal catalysis has enabled bond formation between aryl and olefinic (sp(2)) carbons in a selective and predictable manner with high functional group tolerance. Couplings involving alkyl (sp(3)) carbons have proven more challenging. Here, we demonstrate that the synergistic combination of photoredox catalysis and nickel catalysis provides an alternative cross-coupling paradigm, in which simple and readily available organic molecules can be systematically used as coupling partners. By using this photoredox-metal catalysis approach, we have achieved a direct decarboxylative sp(3)-sp(2) cross-coupling of amino acids, as well as α-O- or phenyl-substituted carboxylic acids, with aryl halides. Moreover, this mode of catalysis can be applied to direct cross-coupling of C(sp³)-H in dimethylaniline with aryl halides via C-H functionalization.
在过去的40年里，过渡金属催化能够以选择性、可预测的方式实现芳基与烯属（sp(2)）碳之间的键形成，且对官能团具有高耐受性。涉及烷基（sp(3)）碳的偶联反应已证明更具挑战性。在此，我们证明光氧化还原催化与镍催化的协同组合提供了一种替代的交叉偶联模式，其中简单且易于获得的有机分子可被系统地用作偶联伙伴。通过使用这种光氧化还原 - 金属催化方法，我们实现了氨基酸以及α - O - 或苯基取代的羧酸与芳基卤化物的直接脱羧sp(3)-sp(2)交叉偶联。此外，这种催化模式可通过C - H官能化应用于二甲基苯胺中C(sp³)-H与芳基卤化物的直接交叉偶联。
