Visible Light-Mediated Intermolecular C-H Functionalization of Electron-Rich Heterocycles with Malonates

被引：300

作者：

Furst, Laura ^{[1
]}

Matsuura, Bryan S. ^{[1
]}

Narayanam, Jagan M. R. ^{[1
]}

Tucker, Joseph W. ^{[1
]}

Stephenson, Corey R. J. ^{[1
]}

机构：

[1] Boston Univ, Dept Chem, Boston, MA 02215 USA

来源：

ORGANIC LETTERS | 2010年 / 12卷 / 13期

关键词：

PHOTOREDOX CATALYSIS; INDOLE-DERIVATIVES; RADICAL-ADDITION; ALPHA-ARYLATION; ALDEHYDES; PYRROLE; ORGANOCATALYSIS; SUBSTITUTION; ALKYLATION; COUPLINGS;

D O I：

10.1021/ol101146f

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The photoredox-mediated direct intermolecular C-H functionalization of substituted indoles, pyrroles, and furans with diethyl bromomalonate is described, utilizing the visible light-induced reductive quenching pathway of Ru(bpy)(3)Cl(2). An analysis of reductive quenchers and mechanistic considerations has led to an optimized protocol for the heteroaromatic alkylations, providing products in good yields and regioselectivities, as well as successfully eliminating previously observed competitive side reactions. This methodology is highlighted by its neutral conditions, activity at ambient temperatures, low catalyst loading, functional group tolerance, and chemoselectivity.

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收藏

页码：3104 / 3107

页数：4

相关论文

共 26 条

[1] Chemoselective Tryptophan Labeling with Rhodium Carbenoids at Mild pH [J].

Antos, John M. ;

McFarland, Jesse M. ;

Iavarone, Anthony T. ;

Francis, Matthew B. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (17) :6301-6308

[2] MN(III)-PROMOTED HOMOLYTIC METHYLMALONYLATION OF PYRROLE AND INDOLE-DERIVATIVES - A SIMPLE ROUTE TO ALPHA-METHYL-2-PYRROLE ACIDS AND ALPHA-METHYL-3-INDOLEACETIC ACIDS [J].

BACIOCCHI, E ;

MURAGLIA, E .

JOURNAL OF ORGANIC CHEMISTRY, 1993, 58 (26) :7610-7612

[3] Tandem radical-electrophilic annulations to pyrrole [J].

Byers, JH ;

DeWitt, A ;

Nasveschuk, CG ;

Swigor, JE .

TETRAHEDRON LETTERS, 2004, 45 (35) :6587-6590

[4] Radical aromatic substitution via atom-transfer addition [J].

Byers, JH ;

Campbell, JE ;

Knapp, FH ;

Thissell, JG .

TETRAHEDRON LETTERS, 1999, 40 (14) :2677-2680

[5] Ruthenium Catalyzed Directing Group-Free C2-Selective Carbenoid Functionalization of Indoles by α-Aryldiazoesters [J].

Chan, Wai-Wing ;

Yeung, Shing-Hin ;

Zhou, Zhongyuan ;

Chan, Albert S. C. ;

Yu, Wing-Yiu .

ORGANIC LETTERS, 2010, 12 (03) :604-607

[6] Visible-Light Photoredox Catalysis: Aza-Henry Reactions via C-H Functionalization [J].

Condie, Allison G. ;

Gonzalez-Gomez, Jose C. ;

Stephenson, Corey R. J. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (05) :1464-+

[7] Catalytic asymmetric Hiyama cross-couplings of racemic α-bromo esters [J].

Dai, Xing ;

Strotman, Neil A. ;

Fu, Gregory C. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (11) :3302-+

[8] Crossed Intermolecular [2+2] Cycloadditions of Acyclic Enones via Visible Light Photocatalysis [J].

Du, Juana ;

Yoon, Tehshik P. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (41) :14604-+

[9] Highly regioselective radical alkylation of 3-substituted pyrroles [J].

Guadarrama-Morales, Oscar ;

Mendez, Francisco ;

Miranda, Luis D. .

TETRAHEDRON LETTERS, 2007, 48 (26) :4515-4518

[10] α-arylation of esters catalyzed by the Pd(I) dimer {[P(t-Bu)3]PdBr}2 [J].

Hama, Takuo ;

Hartwig, John F. .

ORGANIC LETTERS, 2008, 10 (08) :1545-1548