Direct Asymmetric Michael Reaction of α,β-Unsaturated Aldehydes and Ketones Catalyzed by Two Secondary Amine Catalysts

被引：46

作者：

Hayashi, Yujiro ^{[1
]}

Umekubo, Nariyoshi ^{[1
]}

机构：

[1] Tohoku Univ, Grad Sch Sci, Dept Chem, Aoba Ku, 6-3 Aramaki Aza Aoba, Sendai, Miyagi 9808578, Japan

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2018年 / 57卷 / 07期

关键词：

asymmetric synthesis; enamines; Michael reaction; organocatalysis; synthetic methods; ALDOL REACTIONS; SILYL ETHERS; ORGANOCATALYSTS; CONSTRUCTION; REACTIVITIES; ADDITIONS;

D O I：

10.1002/anie.201710085

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A direct asymmetric Michael reaction of alpha,beta-unsaturated aldehydes and ketones proceeded in the presence of two pyrrolidine-type catalysts, a diphenylprolinol silyl ether and hydroxyproline, to afford synthetically useful delta-keto aldehydes with excellent diastereo- and enantioselectivity. Although there are several iminium ions and enamines in the reaction mixture, the iminium ion generated by the former catalyst reacts preferentially with the enamine generated by the latter catalyst.

引用

收藏

页码：1958 / 1962

页数：5

相关论文

共 39 条

[1] OXIDATION OF ALPHA,BETA-UNSATURATED ALDEHYDES [J].

BAL, BS ;

CHILDERS, WE ;

PINNICK, HW .

TETRAHEDRON, 1981, 37 (11) :2091-2096

[2] ASYMMETRIC MICHAEL ADDITIONS - STEREOSELECTIVE ALKYLATIONS OF THE (R)-ENAMINE AND (S)-ENAMINE FROM CYCLOHEXANONE AND 2-(METHOXYMETHYL)PYRROLIDINE BY METHYL ALPHA-(METHOXYCARBONYL)CINNAMATES [J].

BLARER, SJ ;

SEEBACH, D .

CHEMISCHE BERICHTE-RECUEIL, 1983, 116 (06) :2250-2260

[3] Development of a general, enantioselective organocatalytic Mukaiyama-Michael reaction with α,β-unsaturated aldehydes [J].

Borths, Christopher J. ;

Carrera, Diane E. ;

MacMillan, David W. C. .

TETRAHEDRON, 2009, 65 (33) :6746-6753

[4] A New Organocatalytic Concept for Asymmetric α-Alkylation of Aldehydes [J].

Caruana, Lorenzo ;

Kniep, Florian ;

Johansen, Tore Kiilerich ;

Poulsen, Pernille H. ;

Jorgensen, Karl Anker .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2014, 136 (45) :15929-15932

[5]

Donslund B.S., 2015, Angew. Chem, V127, P14066, DOI DOI 10.1002/ANGE.201503920

[6] The Diarylprolinol Silyl Ethers: Ten Years After [J].

Donslund, Bjarke S. ;

Johansen, Tore Kiilerich ;

Poulsen, Pernille H. ;

Halskov, Kim Soholm ;

Jorgensen, Karl Anker .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2015, 54 (47) :13860-13874

[7]

Gotoh H., 2013, SUSTAINABLE CATALYSI, P287

[8] Two Reaction Mechanisms via Iminium Ion Intermediates: The Different Reactivities of Diphenylprolinol Silyl Ether and Trifluoromethyl-Substituted Diarylprolinol Silyl Ether [J].

Gotoh, Hiroaki ;

Uchimaru, Tadafumi ;

Hayashi, Yujiro .

CHEMISTRY-A EUROPEAN JOURNAL, 2015, 21 (35) :12337-12346

[9] Rationally Designed Multifunctional Supramolecular Iminium Catalysis: Direct Vinylogous Michael Addition of Unmodified Linear Dienol Substrates [J].

Gu, Yun ;

Wang, Yao ;

Yu, Tian-Yang ;

Liang, Yong-Min ;

Xu, Peng-Fei .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2014, 53 (51) :14128-14131

[10] One-Pot Sequential Organocatalytic Michael-Tishchenko-Lactonization Reactions. Synthesis of Enantioenriched 4,5,6-Trisubstituted δ-Lactones [J].

Guevara-Pulido, James O. ;

Andres, Jose M. ;

Pedrosa, Rafael .

JOURNAL OF ORGANIC CHEMISTRY, 2014, 79 (18) :8638-8644

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