Catalytic Asymmetric Synthesis of Both Enantiomers of 4‑substituted 1,4-dihydropyridines with the Use of Bifunctional Thiourea-ammonium Salts Bearing Different Counterions

Overview

Journal Molecules

Publisher MDPI

Specialty Biology

Date 2010 Nov 17

PMID 21079568

Citations 3

Authors

Kohzo Yoshida

Tsubasa Inokuma

Kiyosei Takasu

Yoshiji Takemoto

Affiliations

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Abstract

Organoammonium salts composed of a Brønsted acid and an anilinothiourea promoted the Michael addition of ß-keto esters and α,ß-unsaturated aldehydes in the presence of primary amines to give functionalized 1,4-dihydropyridines enantioselectively. With the use of the different Brønsted acids such as DFA and HBF(4) with the same bifunctional thiourea, both enantiomers of 4-substituted 1,4-dihydropyridine were synthesized from the same starting materials.

Citing Articles

Grignard Reagent Addition to Pyridinium Salts: A Catalytic Approach to Chiral 1,4-Dihydropyridines.

Somprasong S, Castineira Reis M, Harutyunyan S ACS Catal. 2024; 14(17):13030-13039.

PMID: 39263543 PMC: 11385375. DOI: 10.1021/acscatal.4c03520.

Chloride-Mediated Alkene Activation Drives Enantioselective Thiourea and Hydrogen Chloride Co-Catalyzed Prins Cyclizations.

Kutateladze D, Wagen C, Jacobsen E J Am Chem Soc. 2022; 144(34):15812-15824.

PMID: 35994741 PMC: 9437134. DOI: 10.1021/jacs.2c06688.

Cooperative Hydrogen-Bond-Donor Catalysis with Hydrogen Chloride Enables Highly Enantioselective Prins Cyclization Reactions.

Kutateladze D, Jacobsen E J Am Chem Soc. 2021; 143(48):20077-20083.

PMID: 34812618 PMC: 8717859. DOI: 10.1021/jacs.1c10890.

References

Taylor M, Jacobsen E . Asymmetric catalysis by chiral hydrogen-bond donors. Angew Chem Int Ed Engl. 2006; 45(10):1520-43. DOI: 10.1002/anie.200503132. View

Wan J, Gan S, Sun G, Pan Y . Novel regioselectivity: three-component cascade synthesis of unsymmetrical 1,4- and 1,2-dihydropyridines. J Org Chem. 2009; 74(7):2862-5. DOI: 10.1021/jo900068z. View

Singh R, Foxman B, Deng L . Asymmetric vinylogous aldol reaction of silyloxy furans with a chiral organic salt. J Am Chem Soc. 2010; 132(28):9558-60. PMC: 2925177. DOI: 10.1021/ja103331t. View

Takemoto Y . Recognition and activation by ureas and thioureas: stereoselective reactions using ureas and thioureas as hydrogen-bonding donors. Org Biomol Chem. 2005; 3(24):4299-306. DOI: 10.1039/b511216h. View

Hamza A, Schubert G, Soos T, Papai I . Theoretical studies on the bifunctionality of chiral thiourea-based organocatalysts: competing routes to C-C bond formation. J Am Chem Soc. 2006; 128(40):13151-60. DOI: 10.1021/ja063201x. View

Jiang J, Yu J, Sun X, Rao Q, Gong L . Organocatalytic asymmetric three-component cyclization of cinnamaldehydes and primary amines with 1,3-dicarbonyl compounds: straightforward access to enantiomerically enriched dihydropyridines. Angew Chem Int Ed Engl. 2008; 47(13):2458-62. DOI: 10.1002/anie.200705300. View

Takemoto Y . Development of chiral thiourea catalysts and its application to asymmetric catalytic reactions. Chem Pharm Bull (Tokyo). 2010; 58(5):593-601. DOI: 10.1248/cpb.58.593. View

Ikariya T, Blacker A . Asymmetric transfer hydrogenation of ketones with bifunctional transition metal-based molecular catalysts. Acc Chem Res. 2007; 40(12):1300-8. DOI: 10.1021/ar700134q. View

Ishihara K, Nakano K . Design of an organocatalyst for the enantioselective Diels-Alder reaction with alpha-acyloxyacroleins. J Am Chem Soc. 2005; 127(30):10504-5. DOI: 10.1021/ja053368a. View

10.

Kitamura M, Suga S, Kawai K, Noyori R . Catalytic asymmetric induction. Highly enantioselective addition of dialkylzincs to aldehydes. J Am Chem Soc. 2011; 108(19):6071-2. DOI: 10.1021/ja00279a083. View

11.

Ikariya T, Murata K, Noyori R . Bifunctional transition metal-based molecular catalysts for asymmetric syntheses. Org Biomol Chem. 2006; 4(3):393-406. DOI: 10.1039/b513564h. View

12.

Vachal P, Jacobsen E . Structure-based analysis and optimization of a highly enantioselective catalyst for the strecker reaction. J Am Chem Soc. 2002; 124(34):10012-4. DOI: 10.1021/ja027246j. View

13.

Bolm C, Rantanen T, Schiffers I, Zani L . Protonated chiral catalysts: versatile tools for asymmetric synthesis. Angew Chem Int Ed Engl. 2005; 44(12):1758-63. DOI: 10.1002/anie.200500154. View

14.

Mita T, Jacobsen E . Bifunctional Asymmetric Catalysis with Hydrogen Chloride: Enantioselective Ring-Opening of Aziridines Catalyzed by a Phosphinothiourea. Synlett. 2010; 2009(10):1680-1684. PMC: 2787453. DOI: 10.1055/s-0029-1217344. View

15.

Dai Q, Yang W, Zhang X . Efficient rhodium-catalyzed asymmetric hydrogenation for the synthesis of a new class of N-aryl beta-amino acid derivatives. Org Lett. 2005; 7(23):5343-5. DOI: 10.1021/ol0523897. View