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

相关论文

共 42 条

[11]

Dudnik AS, 2014, NAT CHEM, V6, P1100, DOI [10.1038/NCHEM.2087, 10.1038/nchem.2087]

[12] Organoborane Catalyzed Regioselective 1,4-Hydroboration of Pyridines [J].

Fan, Xiaoting ;

Zheng, Junhao ;

Li, Zhen Hua ;

Wang, Huadong .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2015, 137 (15) :4916-4919

[13] Catalytic Enantioselective Addition of Dialkylzinc Reagents to N-Acylpyridinium Salts [J].

Fernandez-Ibanez, M. Angeles ;

Macia, Beatriz ;

Pizzuti, Maria Gabriella ;

Minnaard, Adriaan J. ;

Feringa, Ben L. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (49) :9339-9341

[14] Enantioselective N-heterocyclic carbene-catalyzed nucleophilic dearomatization of alkyl pyridiniumst [J].

Flanigan, Darrin M. ;

Rovis, Tomislav .

CHEMICAL SCIENCE, 2017, 8 (09) :6566-6569

[15] Selective Silylative Reduction of Pyridines Leading to Structurally Diverse Azacyclic Compounds with the Formation of sp3 C-Si Bonds [J].

Gandhamsetty, Narasimhulu ;

Park, Sehoon ;

Chang, Sukbok .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2015, 137 (48) :15176-15184

[16] Asymmetric Copper Hydride-Catalyzed Markovnikov Hydrosilylation of Vinylarenes and Vinyl Heterocycles [J].

Gribble, Michael W., Jr. ;

Pirnot, Michael T. ;

Bandar, Jeffrey S. ;

Liu, Richard Y. ;

Buchwald, Stephen L. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2017, 139 (06) :2192-2195

[17] Facile Catalytic Hydrosilylation of Pyridines [J].

Gutsulyak, Dmitry V. ;

van der Est, Art ;

Nikonov, Georgii I. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2011, 50 (06) :1384-1387

[18] Magnesium hydrides and the dearomatisation of pyridine and quinoline derivatives [J].

Hill, Michael S. ;

Kociok-Koehn, Gabriele ;

MacDougall, Dugald J. ;

Mahon, Mary F. ;

Weetman, Catherine .

DALTON TRANSACTIONS, 2011, 40 (46) :12500-12509

[19] Calcium Hydride Catalyzed Highly 1,2-Selective Pyridine Hydrosilylation [J].

Intemann, Julia ;

Bauer, Heiko ;

Pahl, Juergen ;

Maron, Laurent ;

Harder, Sjoerd .

CHEMISTRY-A EUROPEAN JOURNAL, 2015, 21 (32) :11452-11461

[20] Ruthenium-Catalyzed Regioselective 1,4-Hydroboration of Pyridines [J].

Kaithal, Akash ;

Chatterjee, Basujit ;

Gunanathan, Chidambaram .

ORGANIC LETTERS, 2016, 18 (14) :3402-3405

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