Pyridyl Radical Cation for C-H Amination of Arenes

被引：95

作者：

Rossler, Simon L. ^{[1
]}

Jelier, Benson J. ^{[2
]}

Tripet, Pascal F. ^{[2
]}

Shemet, Andrej ^{[1
]}

Jeschke, Gunnar ^{[3
]}

Togni, Antonio ^{[2
]}

Carreira, Erick M. ^{[1
]}

机构：

[1] Swiss Fed Inst Technol, Lab Organ Chem, Vladimir Prelog Weg, CH-8093 Zurich, Switzerland

[2] Swiss Fed Inst Technol, Lab Inorgan Chem, Vladimir Prelog Weg, CH-8093 Zurich, Switzerland

[3] Swiss Fed Inst Technol, Lab Phys Chem, Vladimir Prelog Weg, CH-8093 Zurich, Switzerland

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2019年 / 58卷 / 02期

基金：

加拿大自然科学与工程研究理事会;

关键词：

amination; late-stage functionalization; photoredox catalysis; pyridyl radical cation; radical mechanism; AROMATIC EDA COMPLEXES; PRIMARY AMINES; AMIDATION; IMIDATION; HETEROARENES; SUBSTITUTION; GENERATION; SALTS; PRECURSORS; REACTIVITY;

D O I：

10.1002/anie.201810261

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Electron-transfer photocatalysis provides access to the elusive and unprecedented N-pyridyl radical cation from selected N-substituted pyridinium reagents. The resulting C(sp(2))-H functionalization of (hetero)arenes furnishes versatile intermediates for the development of valuable aminated aryl scaffolds. Mechanistic studies that include the first spectroscopic evidence of a spin-trapped N-pyridyl radical adduct implicate SET-triggered, pseudo-mesolytic cleavage of the N-X pyridinium reagents mediated by visible light.

引用

页码：526 / 531

页数：6

共 74 条

[1] N-Acyloxyphthalimides as Nitrogen Radical Precursors in the Visible Light Photocatalyzed Room Temperature C-H Amination of Arenes and Heteroarenes [J].

Allen, Laura J. ;

Cabrera, Pablo J. ;

Lee, Melissa ;

Sanford, Melanie S. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2014, 136 (15) :5607-5610

[2]

[Anonymous], 2017, ANGEW CHEM

[3]

[Anonymous], 2018, Angew. Chem

[4] Harnessing Alkyl Amines as Electrophiles for Nickel-Catalyzed Cross Couplings via C-N Bond Activation [J].

Basch, Corey H. ;

Liao, Jennie ;

Xu, Jianyu ;

Piane, Jacob J. ;

Watson, Mary P. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2017, 139 (15) :5313-5316

[5] Photochemical Perfluoroalkylation with Pyridine N-Oxides: Mechanistic Insights and Performance on a Kilogram Scale [J].

Beatty, Joel W. ;

Douglas, James J. ;

Miller, Richard ;

McAtee, Rory C. ;

Cole, Kevin P. ;

Stephenson, Corey R. J. .

CHEM, 2016, 1 (03) :456-472

[6] A scalable and operationally simple radical trifluoromethylation [J].

Beatty, Joel W. ;

Douglas, James J. ;

Cole, Kevin P. ;

Stephenson, Corey R. J. .

NATURE COMMUNICATIONS, 2015, 6

[7] Synthesis of 4-functionalized aryl-3,5-diacyl-1,4-dihydropyridines [J].

Bennasar, ML ;

Roca, T ;

Monerris, M ;

Juan, C ;

Bosch, J .

TETRAHEDRON, 2002, 58 (40) :8099-8106

[8] TIME-RESOLVED SPECTROSCOPY AND CHARGE-TRANSFER PHOTOCHEMISTRY OF AROMATIC EDA COMPLEXES WITH X-PYRIDINIUM CATIONS [J].

BOCKMAN, TM ;

LEE, KY ;

KOCHI, JK .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1992, (09) :1581-1594

[9]

Boursalian GB, 2016, NAT CHEM, V8, P810, DOI [10.1038/NCHEM.2529, 10.1038/nchem.2529]

[10] Pd-Catalyzed Aryl C-H Imidation with Arene as the Limiting Reagent [J].

Boursalian, Gregory B. ;

Ngai, Ming-Yu ;

Hojczyk, Katarzyna N. ;

Ritter, Tobias .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2013, 135 (36) :13278-13281

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