Chiral Tertiary Amine Thiourea Research Articles

Synthesis of Chiral Tertiary Amine–Thioureas Based on Spirobi­indane and Application in Catalytic Asymmetric Michael Addition Reaction

A series of novel chiral bifunctional tertiary amine–thioureas based on spirobiindane were designed and synthesized as organo­catalysts. One of these catalysts was shown to promote the asymmetric Michael addition reaction of 1,3-diphenylpropane-1,3-dione to nitro­olefins, affording the desired products in good yields (up to 95%) and enantioselectivities (up to 98% ee).

Highly chemo- and enantioselective vinylogous aldol/cyclization cascade reaction to construct chiral 5,6-dihydropyran-2-ones

An organocatalytic chemo- and enantioselective vinylogous aldol/cyclization cascade reaction between β,γ-unsaturated amides and β,γ-unsaturated α-keto esters was developed. With 5 mol% of chiral tertiary amine-thiourea catalyst C3, highly functionalized 5,6-dihydropyran-2-ones with a quaternary stereocenter were constructed in a straightforward manner with high yields (up to 99%) and excellent enantioselectivities (up to 98% ee).

ChemInform Abstract: Highly Enantio‐ and Diastereoselective [4 + 2] Cycloaddition of 5H‐Oxazol‐4‐ones with N‐Maleimides.

Abstractemploying Takemoto`s chiral tertiary amine‐thiourea as the catalyst

Highly Enantio- and Diastereoselective [4 + 2] Cycloaddition of 5H-oxazol-4-ones with N-Maleimides.

An organocatalytic asymmetric reaction between 5H-oxazol-4-ones and N-substituted maleimides is disclosed. Employing Takemoto's chiral tertiary amine-thiourea as the catalyst, [4 + 2] annulation reactions were performed with high chemoselectivity, leading to a series of biologically important chiral oxo-bridged piperidone-fused succinimides in good to excellent enantioselectivities (up to >99% ee) and >19:1 dr.

Calixarene-derived chiral tertiary amine–thiourea organocatalyzed asymmetric Michael additions of acetyl acetone and dimethyl malonate to nitroolefins

Novel bifunctional chiral thiourea-tertiary amines bearing a calix[4]arene scaffold were synthesized and applied in catalytic asymmetric Michael addition of acetyl acetone and dimethyl malonate to nitroolefins. The corresponding adducts were obtained in excellent yields (up to 99%) and with high enantioselectivities (up to 94% ee).

Enantioselective Construction of Aryl‐Substituted All‐Carbon Quaternary Stereocenters by Using Tertiary Amine–Thiourea‐Catalyzed Michael Additions

AbstractA catalytic enantioselective synthetic strategy for the aryl‐substituted all‐carbon quaternary stereocenters of bioactive hydrodibenzofuran alkaloids was achieved by the Michael addition reaction of α‐cyano ketones and acrylates using a chiral tertiary amine–thiourea catalyst. This method can tolerate steric bulkiness and multiple functional groups, and 32 Michael adducts were prepared in good to excellent yields with moderate to good enantioselectivities. The enantiopurity of the products could also be enriched up to 99 % ee after one recrystallization. This enantioselective Michael addition features a low cost, metal‐free, and easily operable procedure that can provide multifunctionalized enantiopure Michael adducts on a four‐gram scale and supply sufficient amounts of potential precursors for a number of hydrodibenzofuran natural products.

ChemInform Abstract: Direct Enantioselective Amination of α‐Ketoester Catalyzed by Tertiary Amine Thiourea: A new Approach to Chiral α‐Hydroxy‐β‐amino Acid.

Abstract A highly enantioselective amination of α-ketoesters catalyzed by chiral tertiary amine thioureas was reported to afford α-hydroxy-β-amino acids with two continuous stereocenters in high yields (up to 90%) and enantioselectivities (up to 93% ee).

Direct enantioselective amination of α-ketoester catalyzed by tertiary amine thiourea: a new approach to chiral α-hydroxy-β-amino acid

A highly enantioselective amination of α-ketoesters catalyzed by chiral tertiary amine thioureas was reported to afford α-hydroxy-β-amino acids with two continuous stereocenters in high yields (up to 90%) and enantioselectivities (up to 93%ee).

Efficient and highly enantioselective construction of trifluoromethylated quaternary stereogenic centers via high-pressure mediated organocatalytic conjugate addition of nitromethane to β,β-disubstituted enones.

A very effective high-pressure-induced acceleration of asymmetric organocatalytic conjugate addition of nitromethane to sterically congested β,β-disubstituted β-CF3 enones has been developed. A combination of pressure (8-10 kbar) and noncovalent catalysis with low-loading of chiral tertiary amine-thioureas (0.5-3 mol %) is shown to provide very efficient access to a wide range of γ-nitroketones containing trifluoromethylated all-carbon quaternary stereogenic centers in the β-position (80-97%, 92-98% ee).

ChemInform Abstract: An Asymmetric Approach Toward Chiral Multicyclic Spirooxindoles from Isothiocyanato Oxindoles and Unsaturated Pyrazolones by a Chiral Tertiary Amine Thiourea Catalyst.

AbstractThe first organocatalytic Michael‐cyclization cascade reaction between oxindoles (I) and pyrazolones (II) is described.

An asymmetric approach toward chiral multicyclic spirooxindoles from isothiocyanato oxindoles and unsaturated pyrazolones by a chiral tertiary amine thiourea catalyst

The first organocatalytic Michael-cyclization cascade reaction between isothiocyanato oxindoles and unsaturated pyrazolones has been developed. The multicyclic spiro[oxindole/thiobutyrolactam/pyrazolone] core structures containing three contiguous stereogenic centers, including two spiro quaternary centers, were prepared with excellent diastereo- (up to >20 : 1) and enantioselectivities (up to 99% ee).

ChemInform Abstract: Asymmetric Michael Addition of α‐Substituted Isocyanoacetates with Maleimides Catalyzed by Chiral Tertiary Amine Thiourea.

AbstractThe title reaction affords succinimide derivatives having adjacent tertiary and quaternary stereocenters.

Asymmetric Michael Addition of α-Substituted Isocyanoacetates with Maleimides Catalyzed by Chiral Tertiary Amine Thiourea

A highly diastereoselective and enantioselective Michael addition of α-substituted isocyanoacetates with maleimides catalyzed by bifunctional tertiary amine thioureas has been developed. Various chiral succinimide derivatives bearing adjacent quaternary and tertiary stereocenters were prepared in excellent yields (up to 98%), diastereoselectivities (up to 99:1), and enantioselectivities (up to 98% ee). The synthetic utility of chiral succinimide derivatives is also demonstrated in the preparation of h5-HT(1d) receptor agonist motifs.

Highly efficient enantioselective three-component synthesis of 2-amino-4H-chromenes catalysed by chiral tertiary amine-thioureas

A three-component cascade reaction of salicylaldehyde, malononitrile/cyanoacetate and nitromethane catalysed by chiral tertiary amino-thioureas was developed, which leads to the production of highly functionalized 2-amino-4H-chromenes in good yields with good to excellent enantioselectivities.

Asymmetric organocatalytic synthesis of β-Hydroxyynones with a quaternary carbon center under aqueous conditions

The chiral tertiary amine thiourea catalyzed direct aldol reaction of unmodified methyl ynones under aqueous conditions is described. This procedure avoided the retro-aldol reaction of the β-hydroxyynone products, and tolerated both the isatin (1H-indole-2,3-dione) and the less active acyclic α-keto esters as acceptors, affording a structurally diverse array of β-hydroxyynones bearing a quaternary carbon center with moderate to good yields and enantioselectivities.

ChemInform Abstract: Metal‐Free Asymmetric 1,3‐Dipolar Cycloaddition of N‐Arylmaleimides to Azomethine Ylides Catalyzed by Chiral Tertiary Amine Thiourea.

ChemInformVolume 42, Issue 52 Heterocyclic Compounds ChemInform Abstract: Metal-Free Asymmetric 1,3-Dipolar Cycloaddition of N-Arylmaleimides to Azomethine Ylides Catalyzed by Chiral Tertiary Amine Thiourea. Jian-Fei Bai, Jian-Fei Bai Key Lab. Asymmetric Synth. Chirotechnol., Chengdu Inst. Org. Chem., Chin. Acad. Sci., Chengdu 610041, Peop. Rep. ChinaSearch for more papers by this authorLiang-Liang Wang, Liang-Liang Wang Key Lab. Asymmetric Synth. Chirotechnol., Chengdu Inst. Org. Chem., Chin. Acad. Sci., Chengdu 610041, Peop. Rep. ChinaSearch for more papers by this authorLin Peng, Lin Peng Key Lab. Asymmetric Synth. Chirotechnol., Chengdu Inst. Org. Chem., Chin. Acad. Sci., Chengdu 610041, Peop. Rep. ChinaSearch for more papers by this authorYun-Long Guo, Yun-Long Guo Key Lab. Asymmetric Synth. Chirotechnol., Chengdu Inst. Org. Chem., Chin. Acad. Sci., Chengdu 610041, Peop. Rep. ChinaSearch for more papers by this authorJun-Nan Ming, Jun-Nan Ming Key Lab. Asymmetric Synth. Chirotechnol., Chengdu Inst. Org. Chem., Chin. Acad. Sci., Chengdu 610041, Peop. Rep. ChinaSearch for more papers by this authorFei-Ying Wang, Fei-Ying Wang Key Lab. Asymmetric Synth. Chirotechnol., Chengdu Inst. Org. Chem., Chin. Acad. Sci., Chengdu 610041, Peop. Rep. ChinaSearch for more papers by this authorXiao-Ying Xu, Xiao-Ying Xu Key Lab. Asymmetric Synth. Chirotechnol., Chengdu Inst. Org. Chem., Chin. Acad. Sci., Chengdu 610041, Peop. Rep. ChinaSearch for more papers by this authorLi-Xin Wang, Li-Xin Wang Key Lab. Asymmetric Synth. Chirotechnol., Chengdu Inst. Org. Chem., Chin. Acad. Sci., Chengdu 610041, Peop. Rep. ChinaSearch for more papers by this author Jian-Fei Bai, Jian-Fei Bai Key Lab. Asymmetric Synth. Chirotechnol., Chengdu Inst. Org. Chem., Chin. Acad. Sci., Chengdu 610041, Peop. Rep. ChinaSearch for more papers by this authorLiang-Liang Wang, Liang-Liang Wang Key Lab. Asymmetric Synth. Chirotechnol., Chengdu Inst. Org. Chem., Chin. Acad. Sci., Chengdu 610041, Peop. Rep. ChinaSearch for more papers by this authorLin Peng, Lin Peng Key Lab. Asymmetric Synth. Chirotechnol., Chengdu Inst. Org. Chem., Chin. Acad. Sci., Chengdu 610041, Peop. Rep. ChinaSearch for more papers by this authorYun-Long Guo, Yun-Long Guo Key Lab. Asymmetric Synth. Chirotechnol., Chengdu Inst. Org. Chem., Chin. Acad. Sci., Chengdu 610041, Peop. Rep. ChinaSearch for more papers by this authorJun-Nan Ming, Jun-Nan Ming Key Lab. Asymmetric Synth. Chirotechnol., Chengdu Inst. Org. Chem., Chin. Acad. Sci., Chengdu 610041, Peop. Rep. ChinaSearch for more papers by this authorFei-Ying Wang, Fei-Ying Wang Key Lab. Asymmetric Synth. Chirotechnol., Chengdu Inst. Org. Chem., Chin. Acad. Sci., Chengdu 610041, Peop. Rep. ChinaSearch for more papers by this authorXiao-Ying Xu, Xiao-Ying Xu Key Lab. Asymmetric Synth. Chirotechnol., Chengdu Inst. Org. Chem., Chin. Acad. Sci., Chengdu 610041, Peop. Rep. ChinaSearch for more papers by this authorLi-Xin Wang, Li-Xin Wang Key Lab. Asymmetric Synth. Chirotechnol., Chengdu Inst. Org. Chem., Chin. Acad. Sci., Chengdu 610041, Peop. Rep. ChinaSearch for more papers by this author First published: 01 December 2011 https://doi.org/10.1002/chin.201152157Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume42, Issue52December 27, 2011 RelatedInformation

Metal‐Free Asymmetric 1,3‐Dipolar Cycloaddition of N‐Arylmaleimides to Azomethine Ylides Catalyzed by Chiral Tertiary Amine Thiourea

AbstractThe first metal‐free asymmetric 1,3‐dipolar cycloaddition of N‐arylmaleimides to azomethine ylides catalyzed by chiral tertiary amine thiourea to form multiply substituted pyrrolidines in excellent yields (up to 89 %) and enantioselectivities (up to 96 % ee) is presented. This procedure allows a rapid diversity‐oriented synthesis of chiral pyrrolidine derivatives with high optical purity.

ChemInform Abstract: Doubly Stereocontrolled Asymmetric Conjugate Addition of Acetylacetone to Nitroolefins Catalyzed by Bifunctional Tertiary Amine—Thiourea Catalysts Derived from Both Acyclic α‐Amino Acids and Carbohydrates.

Abstract A novel class of easily preparative, cheap, and fine-tunable bifunctional chiral tertiary amine–thiourea organocatalysts have been developed by combining both acyclic diamines derived from acyclic α-amino acids and carbohydrates. These organocatalysts promoted the enantioselective conjugate addition of acetylacetone to various nitroolefins in good yields (up to 93%) with good enantioselectivities (up to 91% ee). The present research demonstrates the advantages of incorporating two stereocontrolling structures into a single catalyst. Notably, it offers a simple and convenient doubly stereocontrolled approach for the catalytic asymmetric synthesis of a chiral organic molecule.

Doubly stereocontrolled asymmetric conjugate addition of acetylacetone to nitroolefins catalyzed by bifunctional tertiary amine–thiourea catalysts derived from both acyclic α-amino acids and carbohydrates

A novel class of easily preparative, cheap, and fine-tunable bifunctional chiral tertiary amine–thiourea organocatalysts have been developed by combining both acyclic diamines derived from acyclic α-amino acids and carbohydrates. These organocatalysts promoted the enantioselective conjugate addition of acetylacetone to various nitroolefins in good yields (up to 93%) with good enantioselectivities (up to 91% ee). The present research demonstrates the advantages of incorporating two stereocontrolling structures into a single catalyst. Notably, it offers a simple and convenient doubly stereocontrolled approach for the catalytic asymmetric synthesis of a chiral organic molecule.

Asymmetric Conjugate Addition of Acetylacetone to Nitroolefins with Chiral Organocatalysts Derived from Both α‐Amino ­Acids and Carbohydrates

AbstractBifunctional chiral tertiary amine thioureas derived from both α‐amino acids and carbohydrates were developed. These organocatalysts promoted the enantioselective conjugate addition of acetylacetone to various aromatic and aliphatic nitroolefins at room temperature in good yields (up to 93 %) and with good enantioselectivity (up to 90 % ee). Furthermore, an interesting matched–mismatched effect of two different chiral units in a chiral organocatalyst was disclosed. Both enantiomers of a product can be achieved in almost the same enantiomeric excess with the “matched” and “mismatched” chiral organocatalysts simply by changing the solvent from THF to toluene. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)