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3. Recent advances in photocatalyzed reactions using well-defined copper(I) complexes

Author

Mingbing Zhong, Xavier Pannecoucke, Philippe Jubault, and Thomas Poisson

Subjects
atra reactions, copper catalysis, energy transfer, oxidation, pcet reactions, photocatalysis, reduction, Science, Organic chemistry, QD241-441
Abstract

This review summarizes the recent advances in photocatalysis using copper complexes. Their applications in various reactions, such as ATRA, reduction, oxidation, proton-coupled electron transfer, and energy transfer reactions are discussed.

Published
2020
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4. Continuous Flow Synthesis of Propofol

Author

Romain Mougeot, Philippe Jubault, Julien Legros, and Thomas Poisson

Subjects
active pharmaceutical ingredient, anesthetics, Friedel–Crafts, decarboxylation, Organic chemistry, QD241-441
Abstract

Herein, we report a continuous flow process for the synthesis of 2,6-diisopropylphenol—also known as Propofol—a short-acting intravenous anesthesia, widely used in intensive care medicine to provide sedation and hypnosis. The synthesis is based on a two-step procedure: a double Friedel–Crafts alkylation followed by a decarboxylation step, both under continuous flow.

Published
2021
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5. Recent Advances for the Direct Introduction of the CF2Me Moiety

Author

Elodie Carbonnel, Thomas Poisson, Philippe Jubault, Xavier Pannecoucke, and Tatiana Besset

Subjects
organofluorine chemistry, synthetic methodology, emergent fluorinated groups, CF2Me-containing reagent, C-CF2Me bond formation, Chemistry, QD1-999
Abstract

Fluorine-containing molecules are compounds of interest in materials as well as in pharmaceutical and agrochemical industries. Therefore, developments in that research field are tremendous and a special focus was dedicated to the design and the study of emergent fluorinated groups. In particular, the CF2Me residue is attractive as it could be used for example as a bioisostere of the methoxy group. Despite the clear asset that represents this fluorinated moiety and in complement to the traditional approaches used to construct the CF2Me residue from existing functional groups, the quest for direct methodologies for the 1,1-difluoroethylation reaction of molecules has triggered a strong interest from the scientific community. This Mini-review will focus on the recent advances toward the design of reagents and their applications for the direct 1,1-difluoroethylation of various classes of compounds.

Published
2019
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8. Phospha-Michael Addition on α-Fluorinated Acrylates: A Straightforward Access to Polyfunctionalized Fine Chemicals

Author

Xin Huang, Tatiana Besset, Philippe Jubault, and Samuel Couve-Bonnaire

Subjects
Acrylates, Organic Chemistry, Stereoisomerism
Abstract

α-Fluorinated acrylates could act as Michael acceptors and become a platform toward the synthesis of relevant complex molecules. Very few conjugate additions have been developed in the literature with these specific substrates, and herein, we reported the first phospha-Michael addition (PMA) on α-trifluoromethylacrylates and α-fluoromethylacrylates. The reaction proved to be highly tolerant and gave original products containing contiguous C-P and C-CFY

Published
2022
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10. Flow synthesis of an α-amino boronic ester as a key precursor of bortezomib drug

Author

Titouan Desrues, Julien Legros, Philippe Jubault, and Thomas Poisson

Subjects
Fluid Flow and Transfer Processes, Chemistry (miscellaneous), Process Chemistry and Technology, Chemical Engineering (miscellaneous), Catalysis
Abstract

The flow synthesis of the optically active α-amino boronate precursor of the bortezomib drug is described, including a key diastereoselective Matteson rearrangement.

Published
2022
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13. Synthesis of Cyclopropylamines through an Electro-Induced Hofmann Rearrangement

Author

Philippe Jubault, Thomas Poisson, André B. Charette, and Thomas Cantin

Subjects
Organic Chemistry, Catalysis
Abstract

A practical access to cyclopropylamines from the corresponding amides is disclosed, according to an electro-induced Hofmann rearrangement. In an undivided cell under galvanostatic conditions, a panel of cyclopropyl amides was readily converted into the corresponding amines (17 examples, 23% to 94% yield). This reaction allowed an easy access to the versatile cyclopropylamines and is complementary to the existing methods.

Published
2023
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14. gem ‐Heteroatom‐Substituted Fluoroalkenes as Mimics of Amide Derivatives or Phosphates: A Comprehensive Review

Author

Jean-Philippe Bouillon, Solène Morand, Philippe Jubault, and Samuel Couve-Bonnaire

Subjects
Steric effects, chemistry.chemical_classification, Geminal, Nitrogen, Isostere, Alkene, Organic Chemistry, Heteroatom, Phosphorus, General Chemistry, Amides, Carbon, Catalysis, Phosphates, chemistry.chemical_compound, chemistry, Amide, Moiety, Organic chemistry, Peptide bond
Abstract

gem-Heteroatom-substituted fluoroalkenes have received little attention despite their great potential in medicinal chemistry or in fine chemistry. Indeed, due to the electronic and steric similarity between the fluoroalkene moiety and the amide bond as well as the high strength of the carbon-fluorine bond, these gem-heteroatom-substituted fluoroalkenes could be envisioned as stable mimics of various important organic functions, such as phosphates, carbamates, S-thiocarbamates and ureas. We present herein an overview describing the syntheses over the last decade of heteroatom-substituted fluoroalkenes in geminal position. This review will be divided into several sections covering each the common following heteroatom: oxygen-, nitrogen-, sulfur-, phosphorus-, boron- and silicon-substituted fluoroalkenes.

Published
2021
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15. Continuous flow synthesis of Celecoxib from 2-bromo-3,3,3-trifluoropropene

Author

Philippe Jubault, Julien Legros, Thomas Poisson, Maria V. Ivanova, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
active pharmaceutical ingredients, Green chemistry, organolithium chemistry, Ketone, oxidation, Alcohol, 010402 general chemistry, 01 natural sciences, Aldehyde, chemistry.chemical_compound, organofluorine chemistry, [CHIM]Chemical Sciences, Fluid Flow and Transfer Processes, chemistry.chemical_classification, Trifluoromethyl, 010405 organic chemistry, Organic Chemistry, Regioselectivity, Organofluorine chemistry, Combinatorial chemistry, Communications, NSAID, 3. Good health, 0104 chemical sciences, chemistry, Chemistry (miscellaneous), Yield (chemistry)
Abstract

Graphical abstract We describe the total flow synthesis of the widely prescribed anti-inflammatory COX-2 inhibitor Celecoxib from 2-bromo-3,3,3-trifluoropropene, as a convenient and available trifluoromethyl building block, to generate trifluoropropynyl lithium and to trap it immediately with an aldehyde. Oxidation of the obtained alcohol into ketone followed by condensation with 4-sulfamidophenylhydrazine afforded the targeted drug with full regioselectivity. It is noteworthy that the quality of these flow reactions (50% overall yield within 1 h cumulated residence time over 3 steps) directly furnished the target API and intermediates with excellent purity. Supplementary Information The online version contains supplementary material available at 10.1007/s41981-021-00205-x.

Published
2021
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16. Organophotocatalysis Enables the Synthesis of

Author

Solène, Morand, William, Lecroq, Philippe, Jubault, Sami, Lakhdar, Jean-Philippe, Bouillon, and Samuel, Couve-Bonnaire

Subjects
Molecular Structure, Alkenes, Catalysis
Published
2022

17. Asymmetric Synthesis of Fluoro, Fluoromethyl, Difluoromethyl, and Trifluoromethylcyclopropanes

Author

Amandine Pons, André B. Charette, Thomas Poisson, Philippe Jubault, and Laetitia Delion

Subjects
chemistry.chemical_compound, Ethyl diazoacetate, chemistry, Nucleophile, Cyclopropanation, Electrophile, Enantioselective synthesis, Diazo, General Medicine, General Chemistry, Combinatorial chemistry, Carbenoid, Cyclopropane
Abstract

Fluorine-containing cyclopropanes are a subclass of cyclopropane derivatives that have generated considerable interest in medicinal chemistry for several decades. The replacement of a cyclopropane C-H or C-CH3 bond with fluorine or a fluorinated group (such as CF3 or CF2H) can lead sometimes to synergistic effects in terms of biological activity and improved metabolic profile of a cyclopropane containing bioactive compound. In this context, the preparation of fluoro-, difluoromethyl-, or trifluoromethyl-cyclopropane is particularly attractive and important but quite challenging considering the unique electronic properties that result from the incorporation of a fluorine atom into a substrate or a reagent. In the past decade, we have sought to develop new routes for the stereoselective synthesis of these building blocks using the most reliable cyclopropanation methods and convenient and readily available starting materials. The challenge that had to be undertaken was how we could use the unique properties of the fluorine atom to improve upon the efficiency of a given process rather than shutting it down. This could be overcome by defining new substrate/reagent reactivity guidelines and carefully selecting whether the fluorinated group was introduced on the electrophilic or nucleophilic partner for a given reaction. In this Account, we describe our contributions in this area that take advantage of diazo-derived rhodium carbenes, zinc carbenoids, ring closure processes, and biocatalytic methods to access these important potential drug subunits. Our initial investigation relied on the development of a Michael-initiated ring closure reaction using the Reformatsky enolate derived from readily available ethyl dibromofluoroacetate and α,β-unsaturated electrophiles. The reaction proceeded extremely well but with modest to good diastereoselectivities with ester acrylates. Further extension to various fluorinated nucleophiles such as oxazolidinone based and DABCO ylides led to similar selectivities.In order to access enantioenriched fluorocyclopropanes, we then investigated the chiral dioxaborolane mediated zinc carbenoid based approaches using the fluoroiodomethylzinc carbenoid/allylic alcohol combination or the iodomethylzinc carbenoid/fluoroallylic alcohol combination. Quite surprisingly, both approaches were equally successful at providing the corresponding fluorocyclopropanes with excellent diastereo- and enantioselectivities.To broaden the scope of fluorinated cyclopropane building blocks that could be prepared with good enantiocontrol, we then investigated the rhodium-catalyzed cyclopropanation of fluoro-, difluoromethyl-, and trifluoromethyl-substituted alkenes with acceptor-acceptor and donor-acceptor diazo reagents. Depending on the substrate/reagent combination, Hashimoto's Rh2((S)-TCPTTL)4 or Davies' Rh2((S)-BTPCP)4 catalyst proved be the most efficient catalysts providing the cyclopropane derivatives with the highest enantioselectivities.More recently, a collaboration with Fasan's group led to the use of engineered myoglobins to catalyze the reaction of ethyl diazoacetate and difluoromethyl-substituted alkenes. This biocatalyzed process led to high turnover number and high enantioselectivities.Although our work has significantly increased the number of tools in the organic chemist's toolbox, continuous efforts in this area would be beneficial to the development of diastereo- and enantioselective approaches to allow the preparation of any elusive isomers of these valuable chiral building blocks.

Published
2021
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18. Copper‐Photocatalyzed Hydrosilylation of Alkynes and Alkenes under Continuous Flow

Author

Xavier Pannecoucke, Philippe Jubault, Thomas Poisson, and Mingbing Zhong

Subjects
chemistry.chemical_compound, chemistry, Hydrosilylation, Continuous flow, Organic Chemistry, Functional group, Photocatalysis, chemistry.chemical_element, General Chemistry, Irradiation, Photochemistry, Copper, Catalysis
Abstract

Herein, the photocatalytic hydrosilylation of alkynes and alkenes under continuous flow conditions is described. By using 0.2 mol % of the developed [Cu(dmp)(XantphosTEPD)]PF6 under blue LEDs irradiation, a large panel of alkenes and alkynes was hydrosilylated in good to excellent yields with a large functional group tolerance. The mechanism of the reaction was studied, and a plausible scenario was suggested.

Published
2021
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19. Copper‐Photocatalyzed Hydroboration of Alkynes and Alkenes

Author

Yohann Gagné, Xavier Pannecoucke, Mathieu Frenette, Philippe Jubault, Mingbing Zhong, Taylor O. Hope, and Thomas Poisson

Subjects
Reaction mechanism, chemistry.chemical_element, 010402 general chemistry, Photochemistry, 01 natural sciences, Redox, Catalysis, chemistry.chemical_compound, hydroboration, boryl radical, continuous flow, Flow Catalysis, Boron, Research Articles, 010405 organic chemistry, General Chemistry, General Medicine, Copper, 0104 chemical sciences, Hydroboration, chemistry, copper, Excited state, Functional group, Photocatalysis, photocatalysis, Research Article
Abstract

The photocatalytic hydroboration of alkenes and alkynes is reported. The use of newly‐designed copper photocatalysts with B2Pin2 permits the formation a boryl radical, which is used for hydroboration of a large panel of alkenes and alkynes. The hydroborated products were isolated in high yields, with excellent diastereoselectivities and a high functional group tolerance under mild conditions. The hydroboration reactions were developed under continuous flow conditions to demonstrate their synthetic utility. The reaction mechanism was studied and suggested an oxidation reaction between an in situ formed borate and the Cu‐photocatalyst in its excited state for the boryl radical formation., We report herein the photocatalytic hydroboration of alkenes and alkynes using newly‐designed copper photocatalysts with B2Pin2. The hydroborated products were obtained under mild conditions in high yields, excellent diastereoselectivities, a high functional group tolerance and developed under continuous flow conditions to demonstrate their synthetic utility. Finally, the reaction mechanism was also studied.

Published
2021
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20. Electrochemical Hydroboration of Alkynes

Author

Philippe Jubault, Thomas Poisson, Maude Aelterman, and Morgane Sayes

Subjects
chemistry.chemical_classification, 010405 organic chemistry, Hydride, Anodic oxidation, Communication, Organic Chemistry, anodic oxidation, Alkyne, chemistry.chemical_element, General Chemistry, 010402 general chemistry, Electrochemistry, alkynes, 01 natural sciences, Combinatorial chemistry, Catalysis, Communications, 0104 chemical sciences, Hydroboration, chemistry, electrochemistry, hydroboration, boryl radical, Boron
Abstract

Herein we reported the electrochemical hydroboration of alkynes by using B2Pin2 as the boron source. This unprecedented reaction manifold was applied to a broad range of alkynes, giving the hydroboration products in good to excellent yields without the need of a metal catalyst or a hydride source. This transformation relied on the possible electrochemical oxidation of an in situ formed borate. This anodic oxidation performed in an undivided cell allowed the formation of a putative boryl radical, which reacted on the alkyne., The electrochemical hydroboration of alkynes by using B2Pin2 as the boron source is reported. This reaction manifold was applied to a broad range of alkynes, giving the hydroboration products in good to excellent yields without the need of a metal catalyst or a hydride source. In addition, the mechanism of this transformation was study.

Published
2021

21. Ru(II)‐Catalyzed Hydroarylation of in situ Generated 3,3,3‐Trifluoro‐1‐propyne by C−H Bond Activation: A Facile and Practical Access to β‐Trifluoromethylstyrenes

Author

Martin Vuagnat, Vincent Tognetti, Philippe Jubault, Tatiana Besset, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), ANR-18-EURE-0020,XL Chem,XLChem, Synthesizing our future(2018), ANR-11-LABX-0029,SYNORG,Synthèse Organique : des molécules au vivant(2011), and European Project: 758710,FarCatCH

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, Catalysis
Abstract

International audience; In this study, a practical and straightforward synthesis of β-( E )-trifluoromethylstyrenes by ruthenium-catalyzed C-H bond activation was developed. The readily available and inexpensive 2-bromo-3,3,3-trifluoropropene (BTP), a non-ozone depleting reagent, was used as a reservoir of 3,3,3-trifluoropropyne. With this approach, the monofunctionalization of a panel of heteroarenes was possible in a safe and scalable manner (23 examples, up to 87% yield). Mechanistic investigations and density functional theory (DFT) calculations were also conducted to get a better understanding of the mechanism of this transformation. These studies suggested that 1) a cyclometallated ruthenium complex enabled the transformation, 2) this latter exhibited high efficiency in this transformation compared to the commercially available [RuCl 2 ( p -cymene)] 2 and 3) the mechanism proceeded through a bis-cyclometallated ruthenium intermediate for the carboruthenation step

Published
2022
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22. Photocatalytic E → Z Contra ‐Thermodynamic Isomerization of Vinyl Silanes with Lewis Base

Author

Thi Minh Thi Le, Thibaud Brégent, Philippe Jubault, and Thomas Poisson

Subjects
Organic Chemistry, General Chemistry, Catalysis
Abstract

Herein, we disclosed the contra-thermodynamic E→Z isomerization of alkenyl silanes, according to the in situ formation of a chromophoric species, in the presence of rac-BINAP as the catalyst. The reaction carried out in DMSO or CH

Published
2022
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23. Continuous-Flow Divergent Lithiation of 2,3-Dihalopyridines: Deprotolithiation versus Halogen Dance

Author

Thibaud Brégent, Maria V. Ivanova, Thomas Poisson, Philippe Jubault, and Julien Legros

Subjects
Organic Chemistry, General Chemistry, Catalysis
Abstract

We describe herein the first halogen dance (HD) in continuous flow on 2-chloro-3-bromopyridine by selectively trapping a (pyridin-4-yl)lithium species that is known to undergo the halogen-dance process. In addition, this lithiated intermediate was trapped at lower temperature before the HD occurs. The HD process was extended to fluoro-iodopyridines by using various electrophiles to afford 28 examples with yields ranging from 42 to 97 % with very short residence times. Finally, scale up of the reaction was demonstrated, affording a promising space-time yield (STY) of 4.2 kg.h

Published
2022

24. Electrochemical Synthesis of gem-Difluoro- and γ-Fluoro-Allyl Boronates and Silanes

Author

Maude Aelterman, Tony Biremond, Philippe Jubault, and Thomas Poisson

Subjects
Organic Chemistry, General Chemistry, Silanes, Catalysis
Abstract

The electrochemical synthesis of fluorinated allyl silanes and boronates was disclosed. The addition of electrogenerated boryl or silyl radicals onto many α-trifluoromethyl or α-difluoromethylstyrenes in an undivided cell allowed the formation of a large panel of synthetically useful gem-difluoro and γ-fluoroallyl boronates and silanes (64 examples, from 31 % to 95 % yield). In addition, a scale up of the reactions under continuous flow was showcased using an electrochemical reactor with promising volumetric productivity (688 g.L

Published
2022

25. Catalytic Asymmetric Syntheses of Alkylidenecyclopropanes from Allenoates with Donor‐Acceptor and Diacceptor Diazo Reagents

Author

Yoko Hasegawa, Thomas Cantin, Jonathan Decaens, Samuel Couve‐Bonnaire, André B. Charette, Thomas Poisson, and Philippe Jubault

Subjects
Organic Chemistry, General Chemistry, Catalysis
Abstract

The first diastereo- and enantioselective cyclopropanation reactions of electron-deficient allenes with donor-acceptor and diacceptor diazo reagents are described. The desired enantioenriched alkylidenecyclopropanes (ACPs) were obtained in high yields with high diastereo- and enantioselectivities in the presence of Rh

Published
2022
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26. Biocatalytic Strategy for the Highly Stereoselective Synthesis of CHF 2 ‐Containing Trisubstituted Cyclopropanes

Author

Daniela M. Carminati, Jonathan Decaens, Samuel Couve‐Bonnaire, Philippe Jubault, and Rudi Fasan

Subjects
010405 organic chemistry, Cyclopropanation, Isostere, Enantioselective synthesis, Total synthesis, General Medicine, General Chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, Ethyl diazoacetate, chemistry, Biocatalysis, Stereoselectivity, Bioisostere
Abstract

The difluoromethyl (CHF2 ) group has attracted significant attention in drug discovery and development efforts, owing to its ability to serve as fluorinated bioisostere of methyl, hydroxyl, and thiol groups. Herein, we report an efficient biocatalytic method for the highly diastereo- and enantioselective synthesis of CHF2 -containing trisubstituted cyclopropanes. Using engineered myoglobin catalysts, a broad range of α-difluoromethyl alkenes are cyclopropanated in the presence of ethyl diazoacetate to give CHF2 -containing cyclopropanes in high yield (up to >99 %, up to 3000 TON) and with excellent stereoselectivity (up to >99 % de and ee). Enantiodivergent selectivity and extension of the method to the stereoselective cyclopropanation of mono- and trifluoromethylated olefins was also achieved. This methodology represents a powerful strategy for the stereoselective synthesis of high-value fluorinated building blocks for medicinal chemistry, as exemplified by the formal total synthesis of a CHF2 isostere of a TRPV1 inhibitor.

Published
2021
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27. Synthesis of Fluoro‐, Monofluoromethyl‐, Difluoromethyl‐, and Trifluoromethyl‐Substituted Three‐Membered Rings

Author

Jonathan Decaens, Samuel Couve-Bonnaire, Philippe Jubault, Thomas Poisson, and André B. Charette

Subjects
chemistry.chemical_compound, Trifluoromethyl, 010405 organic chemistry, Chemistry, Organic Chemistry, Fluorine, chemistry.chemical_element, General Chemistry, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, Catalysis, 0104 chemical sciences
Abstract

This Minireview describes recent advances toward the synthesis of fluoro-, monofluoromethyl-, difluoromethyl-, and trifluoromethyl-substituted three-membered rings such as cyclopropanes, aziridines, epoxides, episulfides, cyclopropenes, and 2 H-azirines. The main synthetic methodologies since 2016 for cyclopropanes and since 2010 for the other three-membered rings are reported.

Published
2020
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28. Synthesis of fluorocyclopropanes via the enantioselective cyclopropanation of fluoro-substituted allylic alcohols using zinc carbenoids

Author

Xavier Pannecoucke, Philippe Jubault, André B. Charette, Laetitia Delion, and Thomas Poisson

Subjects
Allylic rearrangement, Chemistry, Cyclopropanation, Reagent, Organic Chemistry, Enantioselective synthesis, Organic chemistry, chemistry.chemical_element, General Chemistry, Zinc, Catalysis
Abstract

Cyclopropanation reactions using zinc carbenoids are a powerful means to access cyclopropanes. Described herein is an enantioselective version of the reaction using zinc reagents and a chiral dioxaborolane ligand in the generation of fluorocyclopropanes. Readily available 2- and 3-fluoroallylic alcohols were efficiently cyclopropanated in high yields and excellent enantioselectivities. This method provides access to a variety of structurally diverse chiral fluorocyclopropanes that can be used as useful chiral building blocks.

Published
2020
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29. Catalytic Enantioselective Synthesis of Functionalized Cyclopropanes from α‐Substituted Allyl Sulfones with Donor‐Acceptor or Diacceptor Diazo Reagents

Author

Ling Chen, Thi Minh Thi Le, Jean‐Philippe Bouillon, Thomas Poisson, and Philippe Jubault

Subjects
Organic Chemistry, General Chemistry, Catalysis
Abstract

The catalytic asymmetric synthesis of highly functionalized cyclopropanes from α-substituted allyl sulfones and silanes is reported. The reaction, using α-aryl diazoacetates or diacceptor diazo reagents, catalyzed by a chiral rhodium complex (Rh

Published
2022
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32. N ‐Thiocyanato‐2,10‐camphorsultam Derivatives: Design and Applications of Original Electrophilic Thiocyanating Reagents

Author

Philippe Jubault, Martin Vuagnat, Mélissa Gao, Tatiana Besset, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), ANR-11-LABX-0029,SYNORG,Synthèse Organique : des molécules au vivant(2011), ANR-18-EURE-0020,XL Chem,XLChem, Synthesizing our future(2018), and European Project: 758710,FarCatCH

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, Chemistry, Organic Chemistry, Camphorsultam, Combinatorial chemistry, Difunctionalization of alkenes, chemistry.chemical_compound, Electrophilic reagent, Synthetic methods, Reagent, Electrophile, Chiral sources, Physical and Theoretical Chemistry, Thiocyanation
Abstract

International audience; The synthesis of bench-stable electrophilic thiocyanating reagents was depicted in two steps from readily available starting materials in good yields. These newly-designed electrophilic reagents were successfully applied for the thiocyanation of different nucleophiles under mild and transitionmetal-free conditions. Preliminary experiments for the asymmetric C3-thiocyanation of an oxindole derivative were also conducted leading to the expected product with no induction of chirality, although opening possibilities for accessing chiral compounds.

Published
2021
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33. Continuous Flow Synthesis of Propofol

Author

Thomas Poisson, Julien Legros, Philippe Jubault, and Romain Mougeot

Subjects
Decarboxylation, Sedation, Pharmaceutical Science, Organic chemistry, Analytical Chemistry, QD241-441, Hypnosis, Anesthetic, Drug Discovery, anesthetics, active pharmaceutical ingredient, Medicine, Humans, Physical and Theoretical Chemistry, decarboxylation, Propofol, Active ingredient, business.industry, Continuous flow, Communication, Friedel–Crafts, Intravenous anesthesia, Chemistry (miscellaneous), Anesthesia, Anesthesia, Intravenous, Molecular Medicine, medicine.symptom, business, medicine.drug
Abstract

Herein, we report a continuous flow process for the synthesis of 2,6-diisopropylphenol—also known as Propofol—a short-acting intravenous anesthesia, widely used in intensive care medicine to provide sedation and hypnosis. The synthesis is based on a two-step procedure: a double Friedel–Crafts alkylation followed by a decarboxylation step, both under continuous flow.

Published
2021

34. Copper‐Catalyzed Enantioselective Formation of C−CF 3 Centers from β‐CF 3 ‐Substituted Acrylates and Acrylonitriles

Author

Xavier Pannecoucke, Maria V. Ivanova, Thomas Poisson, Philippe Jubault, Pauline Poutrel, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Chemistry, Organic Chemistry, Enantioselective synthesis, hydrides, asymmetric catalysis, chemistry.chemical_element, reduction, General Chemistry, trifluoromethyl group, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Copper, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, copper, Functional group, Copper catalyzed, [CHIM]Chemical Sciences
Abstract

International audience; The catalytic asymmetric synthesis of β‐trifluoromethylated esters or nitriles is reported. The use of an in situ formed chiral Cu−H complex allowed the enantioselective reduction of β‐trifluoromethylated acrylates or acrylonitriles. The reaction proceeds smoothly affording the corresponding enantioenriched products in good to excellent yields and outstanding enantioselectivities (up to 98 % ee). The mechanism of the reaction was studied, and a plausible reaction pathway was suggested accordingly. Finally, the versatility of the products was highlighted through functional group manipulations.

Published
2019
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35. Catalytic Asymmetric Synthesis of α,α-Difluoromethylated and α-Fluoromethylated Tertiary Alcohols

Author

Philippe Jubault, Marie-Léonie Delcourt, Wei-Sheng Huang, Xavier Pannecoucke, André B. Charette, Thomas Poisson, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Centre In Green Chemistry and Catalysis [Montréal] (CCVC), McGill University = Université McGill [Montréal, Canada], Institut Universitaire de France (IUF), and Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.)

Subjects
010405 organic chemistry, Chemistry, Organic Chemistry, Enantioselective synthesis, 010402 general chemistry, 01 natural sciences, Biochemistry, Combinatorial chemistry, 0104 chemical sciences, Catalysis, Dihydroxylation, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Tertiary alcohols
Abstract

International audience; The catalytic asymmetric synthesis of α,α-difluoromethylated tertiary alcohols is described, using an asymmetric dihydroxylation reaction. This protocol using either the AD-mix-α or AD-mix-β allowed an easy access to these valuable fluorinated chiral building blocks, which have been obtained with excellent yields and er. In addition, the reaction was extended to the α-fluoromethylated analogues.

Published
2019
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36. Z -Selective Pd-catalyzed 2,2,2-trifluoroethylation of acrylamides at room temperature

Author

Vijay S. Koshti, Tamás Földesi, Philippe Jubault, Thomas Poisson, Zoltán Novák, Tatiana Besset, Louise Ruyet, Maria I. Lapuh, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institute of Chemistry, Eotvos Lorand University, ANR-11-LABX-0029,SYNORG,Synthèse Organique : des molécules au vivant(2011), ANR-18-EURE-0020,XL Chem,XLChem, Synthesizing our future(2018), European Project: 758710,FarCatCH, Institut de Chimie Organique Fine (IRCOF), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Eötvös Loránd University (ELTE), and ANR-18-EURE-0020,XL Chem,XLChem, Synthesizing our future(2018)

Subjects
Reaction conditions, 010405 organic chemistry, Chemistry, Metals and Alloys, Hypervalent molecule, General Chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry.chemical_compound, Reagent, Yield (chemistry), Functional group, Materials Chemistry, Ceramics and Composites, [CHIM]Chemical Sciences, Stereoselectivity
Abstract

International audience; A straightforward 2,2,2-trifluoroethylation of acrylamides by Pd-catalyzed C–H bond activation was reported by using a fluorinated hypervalent iodine reagent as a coupling partner. At room temperature, this additive-free approach allowed the synthesis of Z-2,2,2-trifluoroethylated acrylamides (19 examples, up to 73% yield) in a stereoselective manner. Under these mild reaction conditions, the methodology turned out to be functional group tolerant and mechanistic studies gave us a better understanding of the transformation.

Published
2021
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38. Biocatalytic Strategy for the Highly Stereoselective Synthesis of CHF

Author

Daniela M, Carminati, Jonathan, Decaens, Samuel, Couve-Bonnaire, Philippe, Jubault, and Rudi, Fasan

Subjects
Cyclopropanes, Hydrocarbons, Fluorinated, Molecular Structure, Myoglobin, Biocatalysis, Stereoisomerism, Article
Abstract

The difluoromethyl (CHF(2)) group has attracted significant attention in drug discovery and development efforts, owing to its ability to serve as fluorinated bioisostere of methyl, hydroxyl, and thiol groups. Herein, we report an efficient biocatalytic method for the highly diastereo- and enantioselective synthesis of CHF(2)-containing trisubstituted cyclopropanes. Using engineered myoglobin catalysts, a broad range of α-difluoromethyl alkenes are cyclopropanated in the presence of ethyl diazoacetate to give CHF(2)-containing cyclopropanes in high yield (up to >99%, up to 3,000 TON) and with excellent stereoselectivity (up to >99% de and ee). By means of an enantiodivergent myoglobin variant, the opposite enantiomer of the cyclopropane product was also obtained. This methodology represents a powerful strategy for the stereoselective synthesis of high-value fluorinated building blocks for medicinal chemistry, as exemplified through the formal total synthesis of a CHF(2) isostere of a TRPV1 inhibitor.

Published
2020

39. Design and Use of Electrophilic Thiocyanating and Selenocyanating Reagents: An Interesting Trend for the Construction of SCN- and SeCN-Containing Compounds

Author

Mu-Yi Chen, Philippe Jubault, Martin Vuagnat, Mélissa Gao, Tatiana Besset, Xavier Pannecoucke, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), ANR-17-CE07-0037,SCoopCH,Vers une catalyse coopérative et éco-compatible pour l'introduction de groupements SRf par fonctionnalisation de liaisons C-H(2017), ANR-10-LABX-0029,IAST,Institut for Advanced Study in Toulouse(2010), European Project: 758710,FarCatCH, Institut de Chimie Organique Fine (IRCOF), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), and Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Chemistry, Organic Chemistry, chemistry.chemical_element, General Chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Sulfur, Catalysis, 0104 chemical sciences, Reagent, Electrophile, Molecule, [CHIM]Chemical Sciences
Abstract

International audience; Organothiocyanate and organoselenocyanate compounds are of paramount importance in organic chemistry as they are key intermediates to access sulfur-and selenium-containing compounds. Therefore, among the different synthetic pathways to get SCN-and SeCN-containing molecules, original methodologies using electrophilic reagents has recently been explored. This Minireview will showcase the recent advances, which have been made. In particular, the design of several electrophilic sources and their applications for the thiocyanation and the selenocyanation of various classes of compounds will be highlighted and discussed.

Published
2020
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40. Organocatalyzed Sulfa-Michael Addition of Thiophenols on Trisubstituted α-Fluoroacrylates, a Straightforward Access to Chiral Fluorinated Compounds

Author

Samuel Couve-Bonnaire, Philippe Jubault, Tatiana Besset, Xin Huang, Emilie David, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and ANR-11-LABX-0029,SYNORG,Synthèse Organique : des molécules au vivant(2011)

Subjects
Addition reaction, biology, 010405 organic chemistry, Dimer, Aryl, Organic Chemistry, Enantioselective synthesis, Cinchona, 010402 general chemistry, biology.organism_classification, 01 natural sciences, Combinatorial chemistry, 3. Good health, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, chemistry, Michael reaction, [CHIM]Chemical Sciences, Tiazesim
Abstract

International audience; In this manuscript, a simple and efficient sulfa-Michael addition reaction of aryl thiols to trisubstituted α-fluoro-α,β-unsaturated esters both in racemic and, for the first time, in enantioselective version is reported. The commercially available dimer of cinchona derivatives (DHQ)2PYR was used as catalyst. This strategy showed a great tolerance for various substrates and substituents, providing fair to excellent yields, moderate to excellent diastereoselectivities (2:1 to > 99:1) and low to good enantioselectivities (2 to 87%). The reaction has been applied to the synthesis of fluorinated analogues of Diltiazem and Tiazesim, both therapeutic agents.

Published
2020
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41. Stereoselective Synthesis of Terminal Monofluoroalkenes from Trifluoromethylated Alkenes

Author

Thomas Poisson, Pauline Poutrel, Xavier Pannecoucke, Philippe Jubault, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Anions, 010405 organic chemistry, Chemistry, Stereochemistry, Organic Chemistry, education, Reaction products, Stereoselectivity, 010402 general chemistry, 01 natural sciences, Biochemistry, humanities, Hydrocarbons, 0104 chemical sciences, Hydrodefluorination, Terminal (electronics), [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Molecular structure
Abstract

International audience; Herein we report the hydrodefluorination reaction of trifluoromethylated alkenes to access terminal monofluoroalkenes. The use of LiAlH4 allowed the stereoselective synthesis of the terminal monofluoroalkenes in good to excellent yields with good to excellent diastereoselectivities. Mechanistic studies suggested a hydroalumination reaction followed by a stereoselective fluoride elimination.

Published
2020
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42. Catalytic Enantioselective Cyclopropanation of α-Fluoroacrylates: An Experimental and Theoretical Study

Author

André B. Charette, Xavier Pannecoucke, Philippe Jubault, Vincent Tognetti, Laurent Joubert, Amandine Pons, Thomas Poisson, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Centre In Green Chemistry and Catalysis [Montréal] (CCVC), and McGill University = Université McGill [Montréal, Canada]

Subjects
cyclopropanes, 010405 organic chemistry, Chemistry, Cyclopropanation, asymmetric synthesis, Enantioselective synthesis, chemistry.chemical_element, General Chemistry, DFT calculations, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Catalysis, 0104 chemical sciences, Rhodium, fluorine, rhodium, Fluorine, [CHIM]Chemical Sciences
Abstract

International audience; Herein, we report the catalytic asymmetric synthesis of functionalized fluorocyclopropanes from α-fluoroacrylates. The method using Rh2((S)-TCPTTL)4 allowed the difficult reaction of an in situ-generated electrophilic Rh-carbene with an electron-poor α-fluoroacrylate. The desired fluorocyclopropanes were obtained in good yields, excellent dr and ee. Finally, the mechanism of this transformation was studied by density functional theory (DFT) calculations to explain the particular reactivity of the donor–acceptor diazo compounds with electron-deficient α-fluoroacrylates.

Published
2019
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43. Practical Synthesis of Ethyl 3-Fluoro-1-pyrrole-2-carboxylate: A Key Fragment of a Potent Drug Candidate against Hepatitis B Virus

Author

Xavier Pannecoucke, Yang Cheng, Philippe Jubault, Pierre Jean-Marie Bernard Raboisson, Maxime Quilan, Jean-François Bonfanti, Thomas Poisson, Jérôme Michel Claude Fortin, Christopher A. Teleha, André B. Charette, Adeline René, Yicheng Deng, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Drug, Hepatitis B virus, 010405 organic chemistry, Fragment (computer graphics), Drug candidate, Chemistry, media_common.quotation_subject, Organic Chemistry, 010402 general chemistry, medicine.disease_cause, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences, 3. Good health, chemistry.chemical_compound, Pyrrole-2-carboxylate, Yield (chemistry), medicine, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, media_common, Pyrrole
Abstract

International audience; We report herein the development of two efficient synthetic routes for the preparation of a key fragment required for the synthesis of potent drug candidates of Hepatitis B virus. The ethyl 3-fluoro-1-H-pyrrole-2-carboxylate scaffold was synthesized from readily available starting materials in good overall yields. The scalability of one of the developed routes was demonstrated and afforded the desired target in good yield and excellent purity (99%).

Published
2019
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44. Copper-Catalyzed Enantioselective Formation of C-CF

Author

Pauline, Poutrel, Maria V, Ivanova, Xavier, Pannecoucke, Philippe, Jubault, and Thomas, Poisson

Abstract

The catalytic asymmetric synthesis of β-trifluoromethylated esters or nitriles is reported. The use of an in situ formed chiral Cu-H complex allowed the enantioselective reduction of β-trifluoromethylated acrylates or acrylonitriles. The reaction proceeds smoothly affording the corresponding enantioenriched products in good to excellent yields and outstanding enantioselectivities (up to 98 % ee). The mechanism of the reaction was studied, and a plausible reaction pathway was suggested accordingly. Finally, the versatility of the products was highlighted through functional group manipulations.

Published
2019

45. Recent Progress Toward the Synthesis of Trifluoromethyl- and Difluoromethyl-Substituted Cyclopropanes

Author

Maxence Bos, Thomas Poisson, André B. Charette, Philippe Jubault, Xavier Pannecoucke, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Trifluoromethyl, 010405 organic chemistry, Organic Chemistry, chemistry.chemical_element, General Chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Catalysis, Cycloaddition, 0104 chemical sciences, 3. Good health, chemistry.chemical_compound, chemistry, Fluorine, [CHIM]Chemical Sciences, Organic chemistry
Abstract

International audience; This Minireview describes recent advances toward the synthesis of trifluoromethyl‐ and difluoromethyl‐substituted cyclopropanes. Synthetic methodologies using [2+1] cycloaddition, ring‐contraction, and ring‐closure cyclopropanations since 2010 are reported.

Published
2017
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46. 18F-Fluoroform: a 18F-trifluoromethylating agent for the synthesis of SCF218F-aromatic derivatives

Author

Daniel Labar, Tatiana Besset, Elodie Carbonnel, Philippe Jubault, Xavier Pannecoucke, Thomas Poisson, ROUX-MERLIN, Madeleine, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Base (chemistry), Fluoroform, Sulfonium, education, Salt (chemistry), chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Catalysis, chemistry.chemical_compound, Derivative (finance), [CHIM] Chemical Sciences, Materials Chemistry, [CHIM]Chemical Sciences, Organic chemistry, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, 010405 organic chemistry, Metals and Alloys, General Chemistry, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry, Ceramics and Composites, Selenium
Abstract

International audience; Herein the synthesis of various SCF218F-containing derivatives is reported by a transition metal-free process. By using HCF218F, readily generated from a bench-stable difluoromethyl sulfonium salt, various aromatic disulfides were easily converted into the desired radiolabelled trifluoromethylthiolated compounds in the presence of a base. This protocol allowed the formation of the SCF218F-containing aromatic derivatives in good to excellent radiochemical yields. This process was also extended to the corresponding selenium derivative.

Published
2017
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47. An electrophilic reagent for the synthesis of OCHFMe-containing molecules

Author

Xavier Pannecoucke, Thomas Poisson, Philippe Jubault, Tatiana Besset, Elodie Carbonnel, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, 010405 organic chemistry, Sulfonium, Metals and Alloys, Salt (chemistry), General Chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry.chemical_compound, chemistry, Reagent, Electrophile, Materials Chemistry, Ceramics and Composites, Thiol, [CHIM]Chemical Sciences, Surface modification, Molecule, Phenols
Abstract

International audience; Herein the synthesis of a novel and bench stable electrophilic reagent to construct the OCFHMe motif from O-nucleophiles has been described. This sulfonium salt, readily obtained in 5 steps, reacted with various phenols and alcohols. The resulting products, including complex molecules, were obtained in good yields. This reagent was also used for the functionalization of thiol derivatives.

Published
2018
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48. Recent Advances for the Direct Introduction of the CF2Me Moiety

Author

Thomas Poisson, Elodie Carbonnel, Philippe Jubault, Xavier Pannecoucke, Tatiana Besset, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), European Project: 758710,FarCatCH, Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
C-CF2Me bond formation, Computer science, emergent fluorinated groups, synthetic methodology, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Nanotechnology, 02 engineering and technology, General Chemistry, CF 2 Me-containing reagent, 010402 general chemistry, 021001 nanoscience & nanotechnology, CF2Me-containing reagent, 01 natural sciences, 0104 chemical sciences, lcsh:Chemistry, chemistry.chemical_compound, Residue (chemistry), lcsh:QD1-999, chemistry, C-CF 2 Me bond formation, organofluorine chemistry, Moiety, Bioisostere, 0210 nano-technology
Abstract

International audience; Fluorine-containing molecules are compounds of interest in materials as well as in pharmaceutical and agrochemical industries. Therefore, developments in that research field are tremendous and a special focus was dedicated to the design and the study of emergent fluorinated groups. In particular, the CF2Me residue is attractive as it could be used for example as a bioisostere of the methoxy group. Despite the clear asset that represents this fluorinated moiety and in complement to the traditional approaches used to construct the CF2Me residue from existing functional groups, the quest for direct methodologies for the 1,1-difluoroethylation reaction of molecules has triggered a strong interest from the scientific community. This Mini-review will focus on the recent advances toward the design of reagents and their applications for the direct 1,1-difluoroethylation of various classes of compounds.

Published
2019
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49. Access to Isothiazolones from Simple Acrylamides by Pd-Catalyzed C–H Bond Activation

Author

Mu-Yi Chen, Xavier Pannecoucke, Tatiana Besset, Philippe Jubault, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), ANR-17-CE07-0037,SCoopCH,Vers une catalyse coopérative et éco-compatible pour l'introduction de groupements SRf par fonctionnalisation de liaisons C-H(2017), European Project: 758710,FarCatCH, Institut de Chimie Organique Fine (IRCOF), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), and Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
C h bond, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Organic Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences, Catalysis, Transition metal, Simple (abstract algebra), Surface modification
Abstract

International audience; A new methodology was developed to access isothiazolone derivatives from simple acrylamides by transition metal catalyzed C–H bond functionalization. This Pd-catalyzed reaction using an electrophilic SCN source offered an efficient tool to access a panel of functionalized isothiazolone derivatives (21 examples, up to 71% yield).

Published
2019
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50. General Catalytic Enantioselective Access to Monohalomethyl and Trifluoromethyl Cyclopropanes

Author

Claire Schlinquer, Xavier Pannecoucke, Thomas Poisson, André B. Charette, Wei-Sheng Huang, Philippe Jubault, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Trifluoromethyl, 010405 organic chemistry, Organic Chemistry, Enantioselective synthesis, chemistry.chemical_element, General Chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Catalysis, 0104 chemical sciences, Rhodium, chemistry.chemical_compound, chemistry, [CHIM]Chemical Sciences, Diazo
Abstract

International audience; An efficient catalytic enantioselective access to chiral functionalized trifluoromethyl cyclopropanes from two classes of diazo compounds and α‐trifluoromethyl styrenes using Rh2((S)‐BTPCP)4 as a catalyst is described. This method provides an efficient and practical strategy for the synthesis of highly functionalized CF3‐cyclopropanes with excellent diastereoselectivities (up to 20:1) and enantioselectivities (up to 99 % ee). The depicted methodology represents, to date, the most efficient catalytic enantioselective method to access highly decorated chiral CF3‐cyclopropanes. Extension to chiral monohalomethyl cyclopropanes in high ee is also reported.

Published
2018
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