Kinetic Resolution of 3-Hydroxy-3-Substituted Oxindoles through NHC-Catalyzed Oxidative Esterification

被引：23

作者：

Lu, Shenci ^{[1
]}

Poh, Si Bei ^{[1
]}

Siau, Woon-Yew ^{[1
]}

Zhao, Yu ^{[1
]}

机构：

[1] Natl Univ Singapore, Dept Chem, Singapore 117543, Singapore

来源：

SYNLETT | 2013年 / 24卷 / 10期

基金：

新加坡国家研究基金会;

关键词：

3-hydroxy-3-substituted oxindoles; asymmetric acylation; kinetic resolution; oxidative NHC catalysis; sequential catalysis; N-HETEROCYCLIC CARBENE; INTERNAL REDOX REACTION; ALPHA; BETA-UNSATURATED ALDEHYDES; COOPERATIVE CATALYSIS; ASYMMETRIC-SYNTHESIS; STEREOSELECTIVE-SYNTHESIS; NUCLEOPHILIC CARBENES; GAMMA-BUTYROLACTONES; TERTIARY ALCOHOLS; ESTERS;

D O I：

10.1055/s-0033-1338745

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The enantioselective synthesis of 3-hydroxy-3-substituted oxindoles has been extensively studied as they represent the core structure of a large number of natural products and pharmaceuticals. While the majority of previous methods focus on the asymmetric addition of different types of nucleophiles to the corresponding ketones, we have reported an unprecedented and alternative approach, namely catalytic kinetic resolution of this important class of tertiary alcohols to provide, for the first time, 3-hydroxy oxindoles with a wide range of 3-substituents including alkyl, alkenyl, alkynyl and aryl groups in highly enantioenriched form. The excellent level of differentiation of the two tertiary alcohol enantiomers (S up to 78) has been realized through oxidative esterification catalyzed by chiral N-heterocyclic carbene (NHC), with the aid of cooperative catalysis by Lewis acid.

引用

页码：1165 / 1169

页数：5

共 56 条

[1] Dihedral angle restriction within a peptide-based tertiary alcohol kinetic resolution catalyst [J].

Angione, Mary C. ;

Miller, Scott J. .

TETRAHEDRON, 2006, 62 (22) :5254-5261

[2]

[Anonymous], 2009, Curr. Bioact. Compd., DOI [10.2174/157340709787580900, DOI 10.2174/157340709787580900]

[3] Dual catalyst control in the enantioselective intramolecular Morita-Baylis-Hillman reaction [J].

Aroyan, CE ;

Vasbinder, MM ;

Miller, SJ .

ORGANIC LETTERS, 2005, 7 (18) :3849-3851

[4] Extending NHC-Catalysis: Coupling Aldehydes with Unconventional Reaction Partners [J].

Biju, Akkattu T. ;

Kuhl, Nadine ;

Glorius, Frank .

ACCOUNTS OF CHEMICAL RESEARCH, 2011, 44 (11) :1182-1195

[5] Organocatalyzed conjugate umpolung of α,β-unsaturated aldehydes for the synthesis of γ-butyrolactones [J].

Burstein, C ;

Glorius, F .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (45) :6205-6208

[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]

Chiang PC, 2011, RSC CATAL SER, P399

[9] Catalytic generation of activated carboxylates:: Direct, stereoselective synthesis of β-hydroxyesters from epoxyaldehydes [J].

Chow, KYK ;

Bode, JW .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (26) :8126-8127

[10] Cooperative Lewis acid/N-heterocyclic carbene catalysis [J].

Cohen, Daniel T. ;

Scheidt, Karl A. .

CHEMICAL SCIENCE, 2012, 3 (01) :53-57

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