Electrophotocatalytic C-H Functionalization of Ethers with High Regioselectivity

被引：154

作者：

Huang, He ^{[1
]}

Strater, Zack M. ^{[2
]}

Lambert, Tristan H. ^{[1
,2
]}

机构：

[1] Cornell Univ, Dept Chem & Chem Biol, Ithaca, NY 14853 USA

[2] Columbia Univ, Dept Chem, New York, NY 10027 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2020年 / 142卷 / 04期

关键词：

HYDROGEN-ATOM TRANSFER; POLARITY-REVERSAL CATALYSIS; DIRECT ARYLATION; RADICALS; ACTIVATION; ALCOHOLS; BONDS;

D O I：

10.1021/jacs.9b11472

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The highly regioselective electrophotocatalytic C-H functionalization of ethers is described. These reactions are catalyzed by a trisaminocyclopropenium (TAC) ion at mild electrochemical potential with visible light irradiation. Ethers undergo oxidant-free coupling with isoquinolines, alkenes, alkynes, pyrazoles, and purines with typically high regioselectivity for the less-hindered alpha-position. The reaction is proposed to operate via hydrogen atom transfer (HAT) from the substrate to the photoexcited TAC radical dication, thus demonstrating a new reactivity mode for this electrophotocatalyst.

引用

页码：1698 / 1703

页数：6

共 46 条

[1] Cross-dehydrogenative coupling of α-C(sp3)-H of ethers/alkanes with C(sp2)-H of heteroarenes under metal-free conditions [J].

Ambala, Srinivas ;

Thatikonda, Thanusha ;

Sharma, Shweta ;

Munagala, Gurunadham ;

Yempalla, Kushalava Reddy ;

Vishwakarma, Ram A. ;

Singh, Parvinder Pal .

ORGANIC & BIOMOLECULAR CHEMISTRY, 2015, 13 (46) :11341-11350

[2]

[Anonymous], 2003, HDB BOND DISSOCIATIO

[3]

[Anonymous], 2007, Hydrogen-Transfer Reactions

[4] SELECTIVE INTERMOLECULAR CARBON-HYDROGEN BOND ACTIVATION BY SYNTHETIC METAL-COMPLEXES IN HOMOGENEOUS SOLUTION [J].

ARNDTSEN, BA ;

BERGMAN, RG ;

MOBLEY, TA ;

PETERSON, TH .

ACCOUNTS OF CHEMICAL RESEARCH, 1995, 28 (03) :154-162

[5]

Bergman RG, 2007, NATURE, V446, P391, DOI 10.1038/446391a

[6] Hydrogen Atom Transfer (HAT): A Versatile Strategy for Substrate Activation in Photocatalyzed Organic Synthesis [J].

Capaldo, Luca ;

Ravelli, Davide .

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2017, 2017 (15) :2056-2071

[7] Complementary Strategies for Directed C(sp3)-H Functionalization: A Comparison of Transition-Metal-Catalyzed Activation, Hydrogen Atom Transfer, and Carbene/Nitrene Transfer [J].

Chu, John C. K. ;

Rovis, Tomislav .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2018, 57 (01) :62-101

[8] The direct arylation of allylic sp3 C-H bonds via organic and photoredox catalysis [J].

Cuthbertson, James D. ;

MacMillan, David W. C. .

NATURE, 2015, 519 (7541) :74-77

[9] Visible light-promoted C-H functionalization of ethers and electron-deficient arenes [J].

Devari, Shekaraiah ;

Shah, Bhahwal Ali .

CHEMICAL COMMUNICATIONS, 2016, 52 (07) :1490-1493

[10] RELATIVE RATES OF H. TRANSFER FROM TRANSITION-METAL HYDRIDES TO TRITYL RADICALS [J].

EISENBERG, DC ;

LAWRIE, CJC ;

MOODY, AE ;

NORTON, JR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (13) :4888-4895

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