Stereoselective 1,3-Insertions of Rhodium(II) Azavinyl Carbenes

被引：195

作者：

Chuprakov, Stepan ^{[1
]}

Worrell, Brady T. ^{[1
]}

Selander, Nicklas ^{[1
]}

Sit, Rakesh K. ^{[1
]}

Fokin, Valery V. ^{[1
]}

机构：

[1] Scripps Res Inst, Dept Chem, La Jolla, CA 92037 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2014年 / 136卷 / 01期

基金：

美国国家科学基金会; 瑞典研究理事会; 美国国家卫生研究院;

关键词：

H INSERTION REACTIONS; RH-CATALYZED TRANSANNULATION; TERMINAL ALKYNES; RING EXPANSION; REACTIVITY; REARRANGEMENTS; CONVERSION; KETONES;

D O I：

10.1021/ja408185c

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Rhodium(II) azavinyl carbenes, conveniently generated from 1-sulfonyl-1,2,3-triazoles, undergo a facile, mild, and convergent formal 1,3-insertion into N-H and O-H bonds of primary and secondary amides, various alcohols, and carboxylic acids to afford a wide range of vicinally bisfunctionalized (Z)-olefins with perfect regio- and stereo-selectivity. Utilizing the distinctive functionality installed through these reactions, a number of subsequent rearrangements and cyclizations expand the repertoire of valuable organic building blocks constructed by reactions of transition-metal carbene complexes, including a-allenyl ketones and amino-substituted heterocycles.

引用

页码：195 / 202

页数：8

共 50 条

[1] A new method for the preparation of silyl enol ethers from carbonyl compounds and (Trimethylsilyl)diazomethane in a regiospecific and highly stereoselective manner [J].

Aggarwal, VK ;

Sheldon, CG ;

Macdonald, GJ ;

Martin, WP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (35) :10300-10301

[2] Conversion of Cyclic Ketones to 2,3-Fused Pyrroles and Substituted Indoles [J].

Alford, Joshua S. ;

Spangler, Jillian E. ;

Davies, Huw M. L. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2013, 135 (32) :11712-11715

[3] Expanding the Scope of Donor/Acceptor Carbenes to N-Phthalimido Donor Groups: Diastereoselective Synthesis of 1-Cyclopropane α-Amino Acids [J].

Alford, Joshua S. ;

Davies, Huw M. L. .

ORGANIC LETTERS, 2012, 14 (23) :6020-6023

[4]

Bagley MC, 1996, SYNLETT, P825

[5] Transition-Metal-Catalyzed Denitrogenative Transannulation: Converting Triazoles into Other Heterocyclic Systems [J].

Chattopadhyay, Buddhadeb ;

Gevorgyan, Vladimir .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2012, 51 (04) :862-872

[6] Rh-Catalyzed Transannulation of N-Tosyl-1,2,3-Triazoles with Terminal Alkynes [J].

Chattopadhyay, Buddhadeb ;

Gevorgyan, Vladimir .

ORGANIC LETTERS, 2011, 13 (14) :3746-3749

[7] Rh-catalyzed transannulation of pyridotriazoles with alkynes and nitriles [J].

Chuprakov, Stepan ;

Hwang, Frank W. ;

Gevorgyan, Vladimir .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (25) :4757-4759

[8] Transannulation of 1-Sulfonyl-1,2,3-triazoles with Heterocumulenes [J].

Chuprakov, Stepan ;

Kwok, Sen Wai ;

Fokin, Valery V. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2013, 135 (12) :4652-4655

[9] Catalytic Asymmetric C-H Insertions of Rhodium(II) Azavinyl Carbenes [J].

Chuprakov, Stepan ;

Malik, Jamal A. ;

Zibinsky, Mikhail ;

Fokin, Valery V. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2011, 133 (27) :10352-10355

[10] Rhodium-Catalyzed Enantioselective Cyclopropanation of Olefins with N-Sulfonyl 1,2,3-Triazoles [J].

Chuprakov, Stepan ;

Kwok, Sen Wai ;

Zhang, Li ;

Lercher, Lukas ;

Fokin, Valery V. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (50) :18034-+

← 1 2 3 4 5 →