Cooperative C(sp3)-H and C(sp2)-H Activation of 2-Ethylpyridines by Copper and Rhodium: A Route toward Quinolizinium Salts

被引：56

作者：

Luo, Ching-Zong ^{[1
]}

Gandeepan, Parthasarathy ^{[1
]}

Wu, Yun-Ching ^{[1
]}

Tsai, Chia-Hung ^{[1
]}

Cheng, Chien-Hong ^{[1
]}

机构：

[1] Natl Tsing Hua Univ, Dept Chem, Hsinchu 30013, Taiwan

来源：

ACS CATALYSIS | 2015年 / 5卷 / 08期

关键词：

rhodium; copper; C-H activation; dehydrogenation; quinolizinium salts; alkynes; H BOND ACTIVATION; CATALYZED AEROBIC DEHYDROGENATION; C-H; INTERNAL ALKYNES; IONIC LIQUIDS; FUNCTIONALIZATION; (HETERO)ARENES; ANNULATION; ARYLATION; ANALOGS;

D O I：

10.1021/acscatal.5b01244

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

A method for the synthesis of substituted quinolizinium salts from 2-ethylpyridines and alkynes is demonstrated. The transformation is conveniently achieved using 1 mol % of a Rh(III) catalyst along with an excess amount of copper(II) salt. The reaction gives high product yields with broad substrate scope and functional group tolerance. Detailed mechanistic studies suggest that 2-vinylpyridine is formed in situ from 2-ethylpyridine by a copper-promoted C(sp(3))-H hydroxylation, followed by dehydration. Later, a Rh(III)-catalyzed pyridine-directed vinylic C(sp(2))-H activation and annulation with alkynes provided the final product.

引用

页码：4837 / 4841

页数：5

共 61 条

[1] Carboxylate-Assisted Ruthenium-Catalyzed Alkyne Annulations by C-H/Het-H Bond Functionalizations [J].

Ackermann, Lutz .

ACCOUNTS OF CHEMICAL RESEARCH, 2014, 47 (02) :281-295

[2] Transition-Metal-Catalyzed Direct Arylation of (Hetero)Arenes by C-H Bond Cleavage [J].

Ackermann, Lutz ;

Vicente, Ruben ;

Kapdi, Anant R. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (52) :9792-9826

[3]

Bond G.C., 2005, Metal-catalysed reactions of hydrocarbons: metals and alloys

[4] AROMATIC CYCLODEHYDRATION .37. QUINOLIZINIUM DERIVATIVES RELATED TO THE PROTOBERBERINE ALKALOIDS [J].

BRADSHER, CK ;

JONES, JH .

JOURNAL OF ORGANIC CHEMISTRY, 1958, 23 (03) :430-431

[5] Synthesis of Pyridine and Dihydropyridine Derivatives by Regio- and Stereoselective Addition to N-Activated Pyridines [J].

Bull, James A. ;

Mousseau, James J. ;

Pelletier, Guillaume ;

Charette, Andre B. .

CHEMICAL REVIEWS, 2012, 112 (05) :2642-2713

[6] Fluorescent quinolizinium ionic liquids (salts) with unexpectedly high quantum yields up to >99% [J].

Chen, Zhengjian ;

Zhang, Shiguo ;

Qi, Xiujuan ;

Liu, Shimin ;

Zhang, Qinghua ;

Deng, Youquan .

JOURNAL OF MATERIALS CHEMISTRY, 2011, 21 (25) :8979-8982

[7] Recent advances in the transition metal-catalyzed twofold oxidative C-H bond activation strategy for C-C and C-N bond formation [J].

Cho, Seung Hwan ;

Kim, Ji Young ;

Kwak, Jaesung ;

Chang, Sukbok .

CHEMICAL SOCIETY REVIEWS, 2011, 40 (10) :5068-5083

[8] Rhodium(III)-catalyzed allylic C-H bond amination. Synthesis of cyclic amines from ω-unsaturated N-sulfonylamines [J].

Cochet, Thomas ;

Bellosta, Veronique ;

Roche, Didier ;

Ortholand, Jean-Yves ;

Greiner, Alfred ;

Cossy, Janine .

CHEMICAL COMMUNICATIONS, 2012, 48 (87) :10745-10747

[9] Rhodium Catalyzed Chelation-Assisted C-H Bond Functionalization Reactions [J].

Colby, Denise A. ;

Tsai, Andy S. ;

Bergman, Robert G. ;

Ellman, Jonathan A. .

ACCOUNTS OF CHEMICAL RESEARCH, 2012, 45 (06) :814-825

[10] Recent Advances in Palladium-Catalyzed C(sp3)-H Activation for the Formation of Carbon-Carbon and Carbon-Heteroatom Bonds [J].

Dastbaravardeh, Navid ;

Christakakou, Maria ;

Haider, Maximilian ;

Schnuerch, Michael .

SYNTHESIS-STUTTGART, 2014, 46 (11) :1421-1439

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