N-Heterocyclic Carbene-Catalyzed Conjugate Additions of Alcohols

被引：185

作者：

Phillips, Eric M. ^{[1
]}

Riedrich, Matthias ^{[1
]}

Scheidt, Karl A. ^{[1
]}

机构：

[1] Northwestern Univ, Dept Chem, Ctr Mol Innovat & Drug Discovery, Chem Life Proc Inst, Evanston, IL 60208 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2010年 / 132卷 / 38期

关键词：

OXY-MICHAEL ADDITIONS; DIELS-ALDER REACTION; ESTERS; THERMOCHEMISTRY; NITROALKENES; UMPOLUNG; HEAT;

D O I：

10.1021/ja1061196

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

An efficient intermolecular conjugate addition of alcohols to activated alkenes catalyzed by N-heterocyclic carbenes has been developed. With 5 mol % of the free carbene derived from IMes center dot HCI, unsaturated ketones and esters are competent substrates, and a variety of primary and secondary alcohols can be employed as the nucleophile. No oligomerization is observed under these mild conditions for effective hydroalkoxylation. In addition to reactions with activated alkenes, IMes catalyzes the formation of vinyl ethers through the 1,4-addition of alcohols to ynones and promotes tandem conjugate addition/Michael cascade reactions. Preliminary data support a Bronsted base mechanism with the free carbene.

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页码：13179 / 13181

页数：3

相关论文

共 49 条

[1] Highly diastereoselective oxy-Michael additions of enantiopure δ-lactol anions to nitroalkenes:: Asymmetric synthesis of 1,2-amino alcohols [J].

Adderley, NJ ;

Buchanan, DJ ;

Dixon, DJ ;

Lainé, DI .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2003, 42 (35) :4241-4244

[2] STABLE CARBENES AS STRONG BASES [J].

ALDER, RW ;

ALLEN, PR ;

WILLIAMS, SJ .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1995, (12) :1267-1268

[3] Formation and stability of N-heterocyclic carbenes in water:: The carbon acid pKa of imidazollum cations in aqueous solution [J].

Amyes, TL ;

Diver, ST ;

Richard, JP ;

Rivas, FM ;

Toth, K .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (13) :4366-4374

[4]

Berkessel A, 2005, ASYMMETRIC ORGANOCATALYSIS: FROM BIOMIMETIC CONCEPTS TO APPLICATIONS IN ASYMMETRIC SYNTHESIS, P1, DOI 10.1002/3527604677

[5] THE BASE-CATALYZED DIMERIZATION OF 3-SUBSTITUTED CYCLOHEXENONES [J].

BUCHI, G ;

HANSEN, JH ;

KNUTSON, D ;

KOLLER, E .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1958, 80 (20) :5517-5524

[6] Cooperative N-Heterocyclic Carbene/Lewis Acid Catalysis for Highly Stereoselective Annulation Reactions with Homoenolates [J].

Cardinal-David, Benoit ;

Raup, Dustin E. A. ;

Scheidt, Karl A. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (15) :5345-+

[7] Conversion of α,β-unsaturated aldehydes into saturated esters:: An umpolung reaction catalyzed by nucleophilic carbenes [J].

Chan, A ;

Scheidt, KA .

ORGANIC LETTERS, 2005, 7 (05) :905-908

[8] Direct amination of homoenolates catalyzed by N-Heterocyclic carbenes [J].

Chan, Audrey ;

Scheidt, Karl A. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (09) :2740-+

[9] Highly stereoselective formal [3+3] cycloaddition of enals and azomethine imines catalyzed by N-heterocyclic carbenes [J].

Chan, Audrey ;

Scheidt, Karl A. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (17) :5334-+

[10] An acidity scale of 1,3-dialkylimidazolium salts in dimethyl sulfoxide solution [J].

Chu, Yuan ;

Deng, Hui ;

Cheng, Jin-Pei .

JOURNAL OF ORGANIC CHEMISTRY, 2007, 72 (20) :7790-7793

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