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Catalytic asymmetric synthesis of 3-(alpha-hydroxy-beta-carbonyl) oxindoles by a Sc(III)-catalyzed direct aldol-type reaction.
Chemistry. 2010 Mar 22; 16(12):3736-42.C

Abstract

A direct catalytic asymmetric aldol-type reaction of 3-substituted-2-oxindoles with glyoxal derivatives and ethyl trifluoropyruvate, catalyzed by a chiral N,N'-dioxide-Sc(OTf)(3) (Tf = trifluoromethanesulfonyl) complex, has been developed that tolerates a wide range of substrates. The reaction proceeds in good yields and excellent enantioselectivities (up to 93% yield, 99:1 diastereomeric ratio (dr), and >99% enantiomeric excess (ee)) under mild conditions, to deliver 3-(alpha-hydroxy-beta-carbonyl) oxindoles with vicinal quaternary-tertiary or quaternary-quaternary stereocenters. Even with 1 mol % catalyst loading or on scaleup (10 mmol of starting material), maintenance of ee was observed, which showed the potential value of the catalyst system. In studies probing the reaction mechanism, a positive nonlinear effect was observed and Sc(III)-based enolate intermediates were detected by using ESIMS. On the basis of the experimental results and previous reports, a possible catalytic cycle was assumed.

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Publisher Full Text (DOI)

Authors+Show Affiliations

Shen K
Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, PR China.
Liu X
No affiliation info available
Zheng K
No affiliation info available
Li W
No affiliation info available
Hu X
No affiliation info available
Lin L
No affiliation info available
Feng X
No affiliation info available

MeSH

CatalysisCoordination ComplexesIndolesMesylatesOxindolesScandiumSpectrometry, Mass, Electrospray IonizationStereoisomerism

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

20175165

Citation

Shen, Ke, et al. "Catalytic Asymmetric Synthesis of 3-(alpha-hydroxy-beta-carbonyl) Oxindoles By a Sc(III)-catalyzed Direct Aldol-type Reaction." Chemistry (Weinheim an Der Bergstrasse, Germany), vol. 16, no. 12, 2010, pp. 3736-42.
Shen K, Liu X, Zheng K, et al. Catalytic asymmetric synthesis of 3-(alpha-hydroxy-beta-carbonyl) oxindoles by a Sc(III)-catalyzed direct aldol-type reaction. Chemistry. 2010;16(12):3736-42.
Shen, K., Liu, X., Zheng, K., Li, W., Hu, X., Lin, L., & Feng, X. (2010). Catalytic asymmetric synthesis of 3-(alpha-hydroxy-beta-carbonyl) oxindoles by a Sc(III)-catalyzed direct aldol-type reaction. Chemistry (Weinheim an Der Bergstrasse, Germany), 16(12), 3736-42. https://doi.org/10.1002/chem.200903471
Shen K, et al. Catalytic Asymmetric Synthesis of 3-(alpha-hydroxy-beta-carbonyl) Oxindoles By a Sc(III)-catalyzed Direct Aldol-type Reaction. Chemistry. 2010 Mar 22;16(12):3736-42. PubMed PMID: 20175165.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Catalytic asymmetric synthesis of 3-(alpha-hydroxy-beta-carbonyl) oxindoles by a Sc(III)-catalyzed direct aldol-type reaction. AU - Shen,Ke, AU - Liu,Xiaohua, AU - Zheng,Ke, AU - Li,Wei, AU - Hu,Xiaolei, AU - Lin,Lili, AU - Feng,Xiaoming, PY - 2010/2/23/entrez PY - 2010/2/23/pubmed PY - 2010/6/30/medline SP - 3736 EP - 42 JF - Chemistry (Weinheim an der Bergstrasse, Germany) JO - Chemistry VL - 16 IS - 12 N2 - A direct catalytic asymmetric aldol-type reaction of 3-substituted-2-oxindoles with glyoxal derivatives and ethyl trifluoropyruvate, catalyzed by a chiral N,N'-dioxide-Sc(OTf)(3) (Tf = trifluoromethanesulfonyl) complex, has been developed that tolerates a wide range of substrates. The reaction proceeds in good yields and excellent enantioselectivities (up to 93% yield, 99:1 diastereomeric ratio (dr), and >99% enantiomeric excess (ee)) under mild conditions, to deliver 3-(alpha-hydroxy-beta-carbonyl) oxindoles with vicinal quaternary-tertiary or quaternary-quaternary stereocenters. Even with 1 mol % catalyst loading or on scaleup (10 mmol of starting material), maintenance of ee was observed, which showed the potential value of the catalyst system. In studies probing the reaction mechanism, a positive nonlinear effect was observed and Sc(III)-based enolate intermediates were detected by using ESIMS. On the basis of the experimental results and previous reports, a possible catalytic cycle was assumed. SN - 1521-3765 UR - https://www.unboundmedicine.com/medline/citation/20175165/Catalytic_asymmetric_synthesis_of_3__alpha_hydroxy_beta_carbonyl__oxindoles_by_a_Sc_III__catalyzed_direct_aldol_type_reaction_ L2 - https://doi.org/10.1002/chem.200903471 DB - PRIME DP - Unbound Medicine ER -