Dual catalysis. Merging photoredox with nickel catalysis: coupling of α-carboxyl sp³-carbons with aryl halides.
Dual catalysis. Merging photoredox with nickel catalysis: coupling of α-carboxyl sp³-carbons with aryl halides.
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DOI：
10.1126/science.1255525
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发表时间：
2014-07-25
期刊：
影响因子：
--
通讯作者：
MacMillan DW
中科院分区：
文献类型：
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作者：
Zuo Z;Ahneman DT;Chu L;Terrett JA;Doyle AG;MacMillan DW
在过去的40年里，过渡金属催化使得芳基碳和烯烃碳（sp2）之间以一种选择性和可预测的方式形成键，具有很高的官能团耐受性。涉及烷基（sp3）碳的偶联已被证明更具挑战性。在这里，我们证明了光氧化还原催化和镍催化的协同组合提供了另一种交叉偶联范式，其中简单易得的有机分子可以系统地用作偶联伙伴。通过这种光氧化还原-金属催化方法，我们已经实现了氨基酸以及α-O -或苯基取代羧酸与芳基卤化物的直接脱羧sp3-sp2交叉偶联。此外，该催化模式可应用于二甲苯胺中Csp3-H与芳基卤化物通过C-H官能化直接交叉偶联。
Over the past 40 years, transition metal catalysis has enabled bond formation between aryl and olefinic (sp2) carbons in a selective and predictable manner with high functional group tolerance. Couplings involving alkyl (sp3) 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 sp3–sp2 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 Csp3–H in dimethylaniline with aryl halides via C–H functionalization.