Asymmetric Cu-Catalyzed 1,4-Dearomatization of Pyridines and Pyridazines without Preactivation of the Heterocycle or Nucleophile

被引：128

作者：

Gribble, Michael W., Jr. ^{[1
]}

Guo, Sheng ^{[1
]}

Buchwald, Stephen L. ^{[1
]}

机构：

[1] MIT, Dept Chem, Cambridge, MA 02139 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2018年 / 140卷 / 15期

基金：

美国国家卫生研究院;

关键词：

ENANTIOSELECTIVE ADDITION; REGIOSELECTIVE 1,4-HYDROBORATION; 1-ACYLPYRIDINIUM SALTS; CONVENIENT METHOD; DEAROMATIZATION; REAGENTS; HYDROSILYLATION; HYDROBORATION; ALKYLATION; ALKYNES;

D O I：

10.1021/jacs.8b02568

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We show that a chiral copper hydride (CuH) complex catalyzes C-C bond-forming dearomatization of pyridines and pyridazines at room temperature. The catalytic reaction operates directly on free hetero-cycles and generates the nucleophiles in situ, eliminating the need for stoichiometric preactivation of either reaction partner; further, it is one of very few methods available for the enantioselective 1,4-dearomatization of heteroarenes. Combining the dearomatization with facile derivatization steps enables one-pot syntheses of enantioenriched pyridines and piperidines.

引用

收藏

页码：5057 / 5060

页数：4

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共 42 条

[31] REACTION OF CUPRATE REAGENTS WITH PYRIDINE IN PRESENCE OF CHLOROFORMATE - NOVEL SYNTHESIS OF 1,4-DIHYDROPYRIDINE DERIVATIVES [J].

PIERS, E ;

SOUCY, M .

CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1974, 52 (20) :3563-3564

[32] Enantioselective addition of activated terminal alkynes to 1-acylpyridinium salts catalyzed by Cu-bis(oxazoline) complexes [J].

Sun, Zhankui ;

Yu, Shouyun ;

Ding, Zuoding ;

Ma, Dawei .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (30) :9300-+

[33] Fully Diastereoselective Synthesis of Polysubstituted, Functionalized Piperidines and Decahydroquinolines Based on Multicomponent Reactions Catalyzed by Cerium(IV) Ammonium Nitrate [J].

Suryavanshi, Padmakar A. ;

Sridharan, Vellaisamy ;

Maiti, Swarupananda ;

Carlos Menendez, J. .

CHEMISTRY-A EUROPEAN JOURNAL, 2014, 20 (28) :8791-8799

[34] Analysis of the Structural Diversity, Substitution Patterns, and Frequency of Nitrogen Heterocycles among US FDA Approved Pharmaceuticals [J].

Vitaku, Edon ;

Smith, David T. ;

Njardarson, Jon T. .

JOURNAL OF MEDICINAL CHEMISTRY, 2014, 57 (24) :10257-10274

[35] Enantioselective CuH-Catalyzed Hydroallylation of Vinylarenes [J].

Wang, Yi-Ming ;

Buchwald, Stephen L. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2016, 138 (15) :5024-5027

[36] Mechanistic Studies of Copper-Catalyzed Asymmetric Hydroboration of Alkenes [J].

Xi, Yumeng ;

Hartwig, John F. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2017, 139 (36) :12758-12772

[37] Face-selective addition to a cation-π complex of a pyridinium salt:: Synthesis of chiral 1,4-dihydropyridines [J].

Yamada, S ;

Morita, C .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (28) :8184-8185

[38] Copper-Catalyzed Enantioselective Addition of Styrene-Derived Nucleophiles to Imines Enabled by Ligand-Controlled Chemoselective Hydrocupration [J].

Yang, Yang ;

Perry, Ian B. ;

Buchwald, Stephen L. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2016, 138 (31) :9787-9790

[39] Enantioselective Copper-Catalyzed Alkylation of Quinoline N-Oxides with Vinylarenes [J].

Yu, Songjie ;

Sang, Hui Leng ;

Ge, Shaozhong .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2017, 56 (50) :15896-15900

[40] Iron-Catalyzed 1,2-Selective Hydroboration of N-Heteroarenes [J].

Zhang, Fanjun ;

Song, Heng ;

Zhuang, Xuewen ;

Tung, Chen-Ho ;

Wang, Wenguang .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2017, 139 (49) :17775-17778

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