Asymmetric Synthesis of Highly Functionalized Tetrahydropyrans via a One-Pot Organocatalytic Michael/Henry/Ketalization Sequence

被引：39
作者：
Hahn, Robert [1 ]
Raabe, Gerhard [1 ]
Enders, Dieter [1 ]
机构：
[1] Rhein Westfal TH Aachen, Inst Organ Chem, D-52074 Aachen, Germany
来源：
ORGANIC LETTERS | 2014年 / 16卷 / 14期
基金：
欧洲研究理事会;
关键词：
DOMINO MICHAEL/ALDOL REACTIONS; STEREOSELECTIVE-SYNTHESIS; CINCHONA ALKALOIDS; CONTIGUOUS STEREOCENTERS; CASCADE REACTIONS; ALDOL REACTION; HENRY REACTION; CONSTRUCTION; CATALYSIS; TANDEM;
D O I：
10.1021/ol501236a
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
A diastereo- and enantioselective Michael/Henry/ketalization sequence to functionalized tetrahydropyrans is described. The multicomponent cascade reaction uses acetylacetone or beta-keto esters, beta-nitrostyrenes, and alkynyl aldehydes as substrates affording tetrahydropyrans with five contiguous stereocenters. Employing a bifunctional quinine-based squaramide organocatalyst, the title compounds are obtained in moderate to good yields (27-80%), excellent enantiomeric excesses (93-99% ee), and high diastereomeric ratios (dr > 20:1) after one crystallization.
引用
收藏
页码：3636 / 3639
页数：4
相关论文
共 115 条
[1]   Enantioselective Mannich-type reaction catalyzed by a chiral Bronsted acid [J].
Akiyama, T ;
Itoh, J ;
Yokota, K ;
Fuchibe, K .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (12) :1566-1568
[2]  
Akiyama T., 2004, ANGEW CHEM INT EDIT, V116, P1592
[3]   Asymmetric Organocatalytic Formal [2+2]-Cycloadditions via Bifunctional H-Bond Directing Dienamine Catalysis [J].
Albrecht, Lukasz ;
Dickmeiss, Gustav ;
Acosta, Fabio Cruz ;
Rodriguez-Escrich, Carles ;
Davis, Rebecca L. ;
Jorgensen, Karl Anker .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (05) :2543-2546
[4]   A Simple Recipe for Sophisticated Cocktails: Organocatalytic One-Pot Reactions-Concept, Nomenclature, and Future Perspectives [J].
Albrecht, Lukasz ;
Jiang, Hao ;
Jorgensen, Karl Anker .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2011, 50 (37) :8492-8509
[5]   Squaramides: Bridging from Molecular Recognition to Bifunctional Organocatalysis [J].
Aleman, Jose ;
Parra, Alejandro ;
Jiang, Hao ;
Jorgensen, Karl Anker .
CHEMISTRY-A EUROPEAN JOURNAL, 2011, 17 (25) :6890-6899
[6]  
[Anonymous], 2008, ANGEW CHEM
[7]   Diversity-Oriented Asymmetric Catalysis (DOAC): Stereochemically Divergent Synthesis of Thiochromanes Using an Imidazoline-Aminophenol-Nickel-Catalyzed Michael/Henry Reaction [J].
Arai, Takayoshi ;
Yamamoto, Yushi .
ORGANIC LETTERS, 2014, 16 (06) :1700-1703
[8]   Organocatalysis - Organocatalysis lost: Modern chemistry, ancient chemistry, and an unseen biosynthetic apparatus [J].
Barbas, Carlos F., III .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2008, 47 (01) :42-47
[9]   Highly enantioselective organocatalytic formation of a quaternary carbon center via chiral Bronsted acid catalyzed self-coupling of enamides [J].
Baudequin, Christine ;
Zamfir, Alexandru ;
Tsogoeva, Svetlana B. .
CHEMICAL COMMUNICATIONS, 2008, (38) :4637-4639
[10]  
BEDORF N, 1993, LIEBIGS ANN CHEM, P1017
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