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

页码：3636 / 3639

页数：4

共 115 条

[61] Organocatalytic tandem Morita-Baylis-Hillman-Michael reaction for asymmetric synthesis of a drug-like oxa-spirocyclic indanone scaffold [J].

Li, Xiang ;

Yang, Lei ;

Peng, Cheng ;

Xie, Xin ;

Leng, Hai-Jun ;

Wang, Biao ;

Tang, Zheng-Wei ;

He, Gu ;

Ouyang, Liang ;

Huang, Wei ;

Han, Bo .

CHEMICAL COMMUNICATIONS, 2013, 49 (77) :8692-8694

[62]

Liu DJ, 2014, GREEN CHEM, V16, P964, DOI [10.1039/c3gc41934g, 10.1039/C3GC41934G]

[63] Asymmetric Organocatalytic Cascade Michael/Hemiketalization/Retro-Aldol Reaction of 2-[(E)-2-Nitrovinyl]phenols with 2,4-Dioxo-4-arylbutanoates: A Convenient Access to Chiral α-Keto Esters [J].

Liu, Yunting ;

Wang, Youming ;

Song, Haibin ;

Zhou, Zhenghong ;

Tang, Chuchi .

ADVANCED SYNTHESIS & CATALYSIS, 2013, 355 (13) :2544-2549

[64] Asymmetric domino synthesis of indanes bearing four contiguous stereocentres catalyzed by sub-mol% loadings of a squaramide in minutes [J].

Loh, Charles C. J. ;

Hack, Daniel ;

Enders, Dieter .

CHEMICAL COMMUNICATIONS, 2013, 49 (87) :10230-10232

[65] Development of Cascade Reactions for the Concise Construction of Diverse Heterocyclic Architectures [J].

Lu, Liang-Qiu ;

Chen, Jia-Rong ;

Xiao, Wen-Jing .

ACCOUNTS OF CHEMICAL RESEARCH, 2012, 45 (08) :1278-1293

[66] The advent and development of organocatalysis [J].

MacMillan, David W. C. .

NATURE, 2008, 455 (7211) :304-308

[67] Chiral Squaramide Derivatives are Excellent Hydrogen Bond Donor Catalysts [J].

Malerich, Jeremiah P. ;

Hagihara, Koji ;

Rawal, Viresh H. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (44) :14416-+

[68] Cinchona-based Primary Amine Catalysis in the Asymmetric Functionalization of Carbonyl Compounds [J].

Melchiorre, Paolo .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2012, 51 (39) :9748-9770

[69] Enantioselective Organocatalytic Diels-Alder Reactions [J].

Merino, Pedro ;

Marques-Lopez, Eugenia ;

Tejero, Tomas ;

Herrera, Raquel P. .

SYNTHESIS-STUTTGART, 2010, (01) :1-26

[70]

Moore J. L., 2010, TOP CURR CHEM, V291, P118

← 2 3 4 5 6 7 8 9 10 11 →