Decarboxylative cross-nucleophile coupling via ligand-to-metal charge transfer photoexcitation of Cu(II) carboxylates

被引:140
作者
Li, Qi Yukki [1 ]
Gockel, Samuel N. [1 ]
Lutovsky, Grace A. [1 ]
DeGlopper, Kimberly S. [1 ]
Baldwin, Neil J. [2 ]
Bundesmann, Mark W. [2 ]
Tucker, Joseph W. [2 ]
Bagley, Scott W. [2 ]
Yoon, Tehshik P. [1 ]
机构
[1] Univ Wisconsin, Dept Chem, 1101 Univ Ave, Madison, WI 53706 USA
[2] Pfizer Inc, Med Design, Groton, CT 06340 USA
关键词
ALPHA-AMINO-ACIDS; COPPER(II)-DICARBOXYLATE COMPLEXES; PHOTOREDOX CATALYSIS; COPPER; FUNCTIONALIZATION; BIOMASS; CONVERSION; ARYLATION; BEHAVIOR; SPECTRA;
D O I
10.1038/s41557-021-00834-8
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Reactions that enable carbon-nitrogen, carbon-oxygen and carbon-carbon bond formation lie at the heart of synthetic chemistry. However, substrate prefunctionalization is often needed to effect such transformations without forcing reaction conditions. The development of direct coupling methods for abundant feedstock chemicals is therefore highly desirable for the rapid construction of complex molecular scaffolds. Here we report a copper-mediated, net-oxidative decarboxylative coupling of carboxylic acids with diverse nucleophiles under visible-light irradiation. Preliminary mechanistic studies suggest that the relevant chromophore in this reaction is a Cu(II) carboxylate species assembled in situ. We propose that visible-light excitation to a ligand-to-metal charge transfer (LMCT) state results in a radical decarboxylation process that initiates the oxidative cross-coupling. The reaction is applicable to a wide variety of coupling partners, including complex drug molecules, suggesting that this strategy for cross-nucleophile coupling would facilitate rapid compound library synthesis for the discovery of new pharmaceutical agents.
引用
收藏
页码:94 / +
页数:7
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