Highly Enantioselective Decarboxylative Mannich Reaction of Malonic Acid Half Oxyesters with Cyclic Trifluoromethyl Ketimines: Synthesis of β‐Amino Esters and Anti‐HIV Drug DPC 083
Chemistry - A European JournalPublished 21 October 2013
Haina Yuan, Shen Li, Jing Nie, Yan Zheng, Jun‐An Ma
Citations97
SJR quartileQ1
SJR score0.98
SNIP0.84
Generate an AI Snapshot to get a quick, structured summary of this paper.
Study Snapshot
ObjectiveStudy objective
MethodsResearch methodology
PopulationPopulation studied
Sample sizeSample sizes
OutcomesStudy outcomes here
ResultsStudy results comes here
LimitationsResearch study limitations comes here
A concise AI-generated summary of the paper will appear here once you click Generate AI Snapshot.
TL;DR
It is demonstrated that cyclic trifluoromethylketimines are highly effective substrates for organocatalytic asymmetric decarboxylative Mannich reaction of MAHOs, providing products in excellent yields and enantioselectivities.
Abstract
An organocatalytic enantioselective decarboxylative Mannich reaction of malonic acid half oxyesters with cyclic ketimines was developed for the preparation of enantioenriched β-amino esters with a quaternary stereogenic center and the anti-HIV drug DPC 083 (see scheme).
Keywords
ChemistryPharmacology, Toxicology and Pharmaceutics
Chemical ReviewsSmall-Molecule H-Bond Donors in Asymmetric Catalysis
2,574 Citations2007Abigail G. Doyle, Eric N. Jacobsen
Angewandte Chemie International EditionAsymmetric Catalysis by Chiral Hydrogen‐Bond Donors
1,900 Citations2006Mark S. Taylor, Eric N. Jacobsen
This review documents the structural and mechanistic features that contribute to high enantioselectivity in hydrogen-bond-mediated catalytic processes in small-molecule, synthetic catalyst systems.
Chemical ReviewsAromatic Trifluoromethylation with Metal Complexes
1,738 Citations2011Olesya A. Tomashenko, Vladimir V. Grushin
Chemical Society ReviewsMetal-free organocatalysis through explicit hydrogen bonding interactions
1,251 Citations2003Peter R. Schreiner
This field is briefly reviewed here, along with some rough guidelines and concepts for further catalyst development, which offers attractive alternatives to metal (ion)-catalyzed reactions by combining supramolecular recognition with chemical transformations in an environmentally benign fashion.
Chemical Society Reviews(Thio)urea organocatalysis—What can be learnt from anion recognition?
1,093 Citations2009Zhiguo Zhang, Peter R. Schreiner
The present critical review outlines the close relationship and mutual interplay between molecular recognition, active site considerations in enzyme catalysis involving anions, and organocatalysis utilizing explicit hydrogen bonding.
Chemical ReviewsAsymmetric Construction of Stereogenic Carbon Centers Featuring a Trifluoromethyl Group from Prochiral Trifluoromethylated Substrates
1,036 Citations2010Jing Nie, Hongchao Guo +2 more
This poster presents a probabilistic analysis of the response of Na6(CO3)(SO4)(SO3) to Na2SO4 using a high-resolution X-ray diffraction analysis for the stationary phase.
Chemical ReviewsCatalytic Enantioselective Formation of C−C Bonds by Addition to Imines and Hydrazones: A Ten-Year Update
964 Citations2011Shu̅ Kobayashi, Yuichiro Mori +2 more
Chemical CommunicationsSelective difluoromethylation and monofluoromethylation reactions
643 Citations2009Jinbo Hu, Wei Zhang +1 more
This feature article summarizes the presently known selective diffluoromethylation and monofluorometHylation methods, including nucleophilic, electrophilic, and free radical di- and mon ofluorometric hylation reagents and reactions.
TetrahedronRecent advances in the stereoselective synthesis of β-amino acids
641 Citations2002Mei Liu, Mukund P. Sibi
Chemistry - An Asian JournalHydrogen‐Bond‐Mediated Asymmetric Catalysis
621 Citations2008Xinhong Yu, Wei Wang
The examples provided neatly demonstrate that chiral ureas and thioureas, diols, and phosphoric acids display effective and unique activation modes of catalysis for a broad spectrum of asymmetric organic transformations, including single-step and multiple-step cascade reactions.
Chemical Society ReviewsOrganocatalysed asymmetric Mannich reactions
580 Citations2007Jorge M. M. Verkade, Lieke J. C. van Hemert +2 more
This tutorial review provides an overview of the recent history of the asymmetric organocatalysed Mannich reaction, including scope and limitations, and application of different catalyst systems.
Chemical ReviewsNovel Syntheses of Azetidines and Azetidinones
567 Citations2008Alberto Brandi, Stefano Cicchi +1 more
Angewandte ChemieAsymmetrische Katalyse durch chirale Wasserstoffbrückendonoren
562 Citations2006Mark S. Taylor, Eric N. Jacobsen
Journal of Fluorine ChemistryStrategies for nucleophilic, electrophilic, and radical trifluoromethylations
558 Citations2007Jun‐An Ma, Dominique Cahard
Chemical Society ReviewsRecent advances in the catalytic asymmetric synthesis of β-amino acids
468 Citations2010Barbara Weiner, Wiktor Szymański +3 more
The progress in catalytic asymmetric synthesis of beta-amino acids is discussed, covering the literature since 2002 and the most important synthetic methods, such as hydrogenation, the Mannich reaction and conjugate additions are covered.
TetrahedronRecent developments in asymmetric catalytic addition to CN bonds
461 Citations2006Gregory K. Friestad, Alex K. Mathies
European Journal of Organic ChemistryOrganocatalytic Asymmetric Mannich Reactions: New Methodology, Catalyst Design, and Synthetic Applications
455 Citations2007Amal Ting, Scott E. Schaus
Angewandte Chemie International EditionTamed Arene and Heteroarene Trifluoromethylation
416 Citations2012Tatiana Besset, Cédric Schneider +1 more
Angewandte Chemie International EditionRecent Developments in the Catalytic Asymmetric Synthesis of α‐ and β‐Amino Acids
380 Citations2003Jun‐An Ma
This minireview collects recent work on catalytic asymmetric synthesis of alpha- and beta-amino acids.
ScienceBroad-Spectrum, Non-Opioid Analgesic Activity by Selective Modulation of Neuronal Nicotinic Acetylcholine Receptors
370 Citations1998Anthony W. Bannon, Michael Decker +10 more
Tetrahedron AsymmetryRecent advances in enantioselective trifluoromethylation reactions
345 Citations2008Norio Shibata, Satoshi Mizuta +1 more
Journal of the American Chemical SocietyPolyoxins, antifungal antibiotics. XIII. Structure of polyoxins
344 Citations1969Kiyoshi Isono, Ken‐ichi Asahi +1 more
Journal of Medicinal ChemistryInhibition of Clinically Relevant Mutant Variants of HIV-1 by Quinazolinone Non-Nucleoside Reverse Transcriptase Inhibitors
301 Citations2000Jeffrey W. Corbett, Soo S. Ko +13 more
The increased potency of these NRTIs is combined with favorable plasma serum protein binding as demonstrated by improvements in the percent free drug in human plasma when compared to efavirenz.
Accounts of Chemical Researchα-Trifluoromethylated Carbanion Synthons
259 Citations2008Kenji Uneyama, Toshimasa Katagiri +1 more
A well-designed device for the generation, stabilization, and acceleration for alkylation of the alpha-trifluoromethylated carbanions is needed for their synthetic application, as well as stabilization by the electron-withdrawing alpha-substituent.
Organic LettersHighly Enantioselective Michael Addition of Aromatic Ketones to Nitroolefins Promoted by Chiral Bifunctional Primary Amine-thiourea Catalysts Based on Saccharides
222 Citations2007Kun Liu, Han‐Feng Cui +4 more
A new class of thiourea catalysts have been developed which integrate saccharide and primary amine moieties into one small organic molecule and are shown to be highly enantioselective for direct addition of aromatic ketones to a range of nitrooleolefins.
Chemistry - A European JournalEnantioselective Organocatalytic Synthesis of Fluorinated Molecules
219 Citations2011Guillem Valero, Xavier Companyó +1 more
The main aim of this review is to cover the most important organocatalytic enantioselective methodologies to obtain fluorinated molecules, giving the catalysts, mechanisms and reagents that have been used.
Chemistry - A European JournalEnantioselective Synthesis of AG‐041R by using <i>N</i>‐Heteroarenesulfonyl Cinchona Alkaloid Amides as Organocatalysts
206 Citations2012Noriyuki Hara, Shuichi Nakamura +4 more
X-ray crystallographic analysis revealed that the hydrogen bonding between the sulfonimide proton and the 8-quinolyl nitrogen atom plays an important role in exerting the enantioselectivity of the reaction.
Chemical Society ReviewsProgress in fluoroalkylation of organic compounds via sulfinatodehalogenation initiation system
199 Citations2012Cheng‐Pan Zhang, Qing‐Yun Chen +3 more
With the increasing demands to utilize the unique properties of fluorine and fluorinated functional groups in medicinal, agricultural and material sciences, it is believed that there will continue to be useful developments in sulfinatodehalogenation chemistry and it will be applied more widely in the future.
ChemInformHighly Enantioselective Michael Addition of Aromatic Ketones to Nitroolefins Promoted by Chiral Bifunctional Primary Amine‐Thiourea Catalysts Based on Saccharides.
186 Citations2007Kun Liu, Han‐Feng Cui +4 more
Biochemical JournalAzetidine-2-carboxylic acid: a new cyclic imino acid occurring in plants
173 Citations1956L. Fowden
Angewandte Chemie International EditionHydrogen‐Bond‐Directed Enantioselective Decarboxylative Mannich Reaction of β‐Ketoacids with Ketimines: Application to the Synthesis of Anti‐HIV Drug DPC 083
163 Citations2013Haina Yuan, Shuai Wang +4 more
This is the first hydrogen-bond-directed enantioselective decarboxylative Mannich reaction of β-ketoacids with ketimines affording quinazolinone derivatives with quaternary stereocenters in high yields and with excellent enantiOSElectivities using saccharide-based amino-thiourea organocatalysts.
Advanced Synthesis & CatalysisCombination Catalysis in Enantioselective Trifluoromethylation
144 Citations2010Yan Zheng, Jun‐An Ma
Angewandte ChemieDie Trifluormethylierung von Arenen und Heteroarenen
130 Citations2012Tatiana Besset, Cédric Schneider +1 more
Angewandte Chemie International EditionBifunctional Cinchona Alkaloid Thiourea Catalyzed Highly Efficient, Enantioselective Aza‐Henry Reaction of Cyclic Trifluoromethyl Ketimines: Synthesis of Anti‐HIV Drug DPC 083
128 Citations2011Hexin Xie, Yinan Zhang +3 more
Bifunctional Cinchona Alkaloid Thiourea Catalyzed Highly Efficient, Enantioselective Aza-Henry Reaction of Cyclic Trifluoromethyl Ketimines: Synthesis of Anti-HIV Drug DPC 083 Angew.
Advanced Synthesis & CatalysisOrganocatalytic Enantioselective Decarboxylative Addition of Malonic Half Thioesters to Imines
117 Citations2007Alfredo Ricci, Daniel Pettersen +5 more
A biomimetic organocatalytic enantioselective decarboxylative addition of malonic acid half thioesters to imines is described, being attractive precursors for the preparation of optically active β-amino acids.
The Journal of Organic ChemistryChiral Bifunctional Thiourea-Catalyzed Enantioselective Michael Addition of Ketones to Nitrodienes
106 Citations2010Hai Ma, Kun Liu +4 more
Simple bifunctional thioureas, derived from the commercially available saccharides and chiral diamines, have been shown tunably to promote Michael-type addition of ketones to alpha,beta-gamma,delta-nitrodienes.
ChemCatChemH‐Donor Anion Acceptor Organocatalysis—The Ionic Electrophile Activation Approach
100 Citations2012Stephan Beckendorf, Sören Asmus +1 more
Hydrogen bonds are key interactions in nature, which create cooperative non-covalent networks that support highly efficient molecular transformations that support high selective substrate recognition, activation, and elevated stereocontrol in enzyme catalysis.
Chemistry - A European JournalExpanding the Utility of Brønsted Base Catalysis: Biomimetic Enantioselective Decarboxylative Reactions
99 Citations2011Yuanhang Pan, Choon Wee Kee +6 more
It is proposed that nucleophilic addition precedes decarboxylation in the mechanism, which has been investigated in detail through the identification of intermediates by using electrospray ionization (ESI) mass-spectrometric analysis and DFT calculations.
Advanced Synthesis & CatalysisHighly Enantioselective Construction of a Quaternary Carbon Center of Dihydroquinazoline by Asymmetric Mannich Reaction and Chiral Recognition
94 Citations2008Biao Jiang, Jiajia Dong +4 more
Angewandte ChemieNeuere Entwicklungen in der katalytischen asymmetrischen Synthese von α‐ und β‐Aminosäuren
90 Citations2003Jun‐An Ma
ChemInformOrganocatalytic Enantioselective Decarboxylative Addition of Malonic Half Thioesters to Imines.
88 Citations2007Alfredo Ricci, Daniel Pettersen +5 more
Chemical CommunicationsHighly enantioselective organocatalytic Strecker reaction of cyclic N-acyl trifluoromethylketimines: synthesis of anti-HIV drug DPC 083
81 Citations2012Fa‐Guang Zhang, Xiaoyan Zhu +3 more
A highly efficient, organocatalytic, enantioselective Strecker reaction of cyclic N-acyl ketimines was developed for the preparation of enantioenriched cyclic α-amino nitriles with a quaternary carbon stereocentre and anti-HIV drug DPC 083.
Chemistry - A European JournalHighly Diastereo‐ and Enantioselective Organocatalytic One‐Pot Sequential 1,4‐Addition/Dearomative‐Fluorination Transformation
79 Citations2012Feng Li, Long Sun +4 more
Fluorination: A wide range of nitroolefins and pyrazol-5-ones undergo a sequential 1,4-addition/dearomative-fluorination transformation when treated with a catalytic amount of a tertiary-amine-thiourea compound and the terminal electrophile to give fluorinated products in 72-95% yield with up to 99:1 d.r. and 98% ee.
Organic LettersA Highly Diastereoselective Decarboxylative Mannich Reaction of β-Keto Acids with Optically Active <i>N</i>-Sulfinyl α-Imino Esters
78 Citations2012Cuifeng Yang, Chen Shen +2 more
Preliminary mechanistic studies indicate that the reaction proceeds through imine addition followed by decarboxylation.
The Journal of Organic ChemistryOrganocatalytic Asymmetric One-Pot Sequential Conjugate Addition/Dearomative Fluorination: Synthesis of Chiral Fluorinated Isoxazol-5(4<i>H</i>)-ones
66 Citations2012Wen‐Ting Meng, Yan Zheng +3 more
A facile one-pot sequential conjugate addition/dearomative fluorination transformation of isoxazol-5(4H)-ones with nitroolefins and N-fluorobenzenesulfonimide (NFSI) has been developed by using a bifunctional chiral tertiary amino-thiourea catalyst.
Green ChemistryEnvironmentally benign metal-free decarboxylative aldol and Mannich reactions
64 Citations2009Jérôme Baudoux, Pierre Lefebvre +3 more
Aiming at the development of green and efficient C–C bond formations (aldol and Mannich reactions), the decarboxylative nucleophilic addition of malonic acid half ester to imines or aldehydes under mild metal-free conditions was studied and revealed two distinct mechanisms depending on the hemimalonate used.
Beilstein Journal of Organic ChemistryAsymmetric organocatalytic decarboxylative Mannich reaction using β-keto acids: A new protocol for the synthesis of chiral β-amino ketones
49 Citations2012Chunhui Jiang, Fangrui Zhong +1 more
The first decarboxylative Mannich reaction employing β-keto acids, catalyzed by cinchonine-derived bifunctional thiourea catalyst has been described and the desired β-amino ketones were obtained in excellent yields and with moderate to good enantioselectivities.
Angewandte ChemieHydrogen‐Bond‐Directed Enantioselective Decarboxylative Mannich Reaction of β‐Ketoacids with Ketimines: Application to the Synthesis of Anti‐HIV Drug DPC 083
49 Citations2013Haina Yuan, Shuai Wang +4 more
SynthesisCatalytic Decarboxylative Reactions: Biomimetic Approaches Inspired by Polyketide Biosynthesis
46 Citations2011Choon‐Hong Tan, Yuanhang Pan
Angewandte ChemieBifunctional Cinchona Alkaloid Thiourea Catalyzed Highly Efficient, Enantioselective Aza‐Henry Reaction of Cyclic Trifluoromethyl Ketimines: Synthesis of Anti‐HIV Drug DPC 083
35 Citations2011Hexin Xie, Yinan Zhang +3 more
Journal of Fluorine ChemistryChiral bifunctional thiourea-catalyzed enantioselective aldol reaction of trifluoroacetaldehyde hemiacetal with aromatic ketones
32 Citations2011Jing Nie, Xiaojuan Li +4 more
Tetrahedron LettersMolecular sieve mediated decarboxylative Mannich and aldol reactions of β-ketoacids
31 Citations2013Fangrui Zhong, Chunhui Jiang +3 more
An analogous molecular sieve promoted decarboxylative aldol reaction between β-ketoacids and isatins is also described, which affords bioactive 3-substituted-3-hydroxy-oxindoles in excellent yields.