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149 results on '"Laurent Micouin"'

1. Diastereoselective Ring Homologation of Bicyclic Hydrazines: Access to cis-1,3-Diaminocyclohexitols

Author: Aurélie Blond, Serge Turcaud, Thomas Lecourt, and Laurent Micouin
Subjects: Chemistry, QD1-999
Published: 2018
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2. Light-Driven Reductive Cleavage of Sulfonamides Promoted by Thiourea Organophotosensitizers

Author: Jules Brom, Antoine Maruani, Laurent Micouin, and Erica Benedetti
Subjects: Organic Chemistry
Abstract: We have developed a practical method to perform the reductive photocleavage of sulfonamides using thioureas as organophotocatalysts. This transformation, which tolerates a variety of substrates, occurs under mild reaction conditions in the presence of tetrabutylammonium borohydride as a reducing agent. Experimental and theoretical mechanistic investigations complete the study, shedding light on the nature of the active species involved in the photocatalytic process.
Published: 2023

3. Compact CPL emitters based on a [2.2]paracyclophane scaffold: recent developments and future perspectives

Author: Simon Felder, Marie-Leonie Delcourt, Damian Contant, Rafael Rodríguez, Ludovic Favereau, Jeanne Crassous, Laurent Micouin, Erica Benedetti, Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Agence Nationale de la Recherche (ANR PhotoChiraPhane), CNRS, IdEx Universite Paris Cite (pCpPhotoCat), Universite de Rennes 1, Ministere de l'Enseignement Superieur et de la Recherche, Xunta de Galicia, and ANR-19-CE07-0001,PhotoChiraPhane,Synthèse et applications de catalyseurs photoredox à chiralité planaire dérivés du [2.2]paracyclophane(2019)
Subjects: Materials Chemistry, [CHIM]Chemical Sciences, General Chemistry
Abstract: International audience; Due to their unique three-dimensional framework and intriguing electronic properties, [2.2]paracyclophanes (pCps) have been employed over the years as building blocks in materials science for the development of organic light-emitting diodes and non-linear optical systems. In addition, depending on their substitution patterns, [2.2]paracyclophanes can display planar chirality and are nowadays considered as useful scaffolds for the development of original circularly poliarized luminescence (CPL) emitters. This perspective gives an overview on the synthesis and characterization of different families of compact luminescent compounds derived from planar chiral [2.2]paracyclophanes. The chiroptical properties of these small molecules are described, with a particular focus on their ability to emit circularly polarized luminescence in solution. Some future prospects on the design and potential applications of CPL emitters derived from pCps are finally presented.
Published: 2023

4. PSL Chemical Biology Symposia Third Edition: A Branch of Science in its Explosive Phase

Author: Leeroy Baron, Justine Hadjerci, Leishemba Thoidingjam, Marina Plays, Romain Bucci, Nolwenn Morris, Sebastian Müller, Fabien Sindikubwabo, Stéphanie Solier, Tatiana Cañeque, Ludovic Colombeau, Cedric M. Blouin, Christophe Lamaze, Alain Puisieux, Yannick Bono, Christine Gaillet, Luca Laraia, Boris Vauzeilles, Frédéric Taran, Sébastien Papot, Philippe Karoyan, Romain Duval, Florence Mahuteau‐Betzer, Paola Arimondo, Kevin Cariou, Gilles Guichard, Laurent Micouin, Mélanie Ethève‐Quelquejeu, Daniela Verga, Antoine Versini, Gilles Gasser, Cong Tang, Philippe Belmont, Andreas Linkermann, Claudia Bonfio, Dennis Gillingham, Thomas Poulsen, Marco Di Antonio, Marie Lopez, Dominique Guianvarc'h, Christophe Thomas, Géraldine Masson, Arnaud Gautier, Ludger Johannes, and Raphaël Rodriguez
Subjects: Organic Chemistry, Molecular Medicine, Molecular Biology, Biochemistry
Published: 2023

5. Intramolecular Buchwald-Hartwig N-Arylation of Bicyclic Hydrazines: Practical Access to Spiro[indoline-2,3'-piperidines]

Author: Claire Fleurisson, Nessrine Graidia, Yann Foricher, Erica Benedetti, and Laurent Micouin
Subjects: Organic Chemistry, Physical and Theoretical Chemistry, Biochemistry
Abstract: In recent years, spirocycles have been the focus of medicinal chemistry, and several drugs or drug candidates incorporating these “non-planar” chemical motifs have been developed. New advancements in this field, however, are greatly limited by the lack of innovative methods enabling the preparation of original spirocyclic cores. Here-in, an unprecedented intramolecular Buchwald-Hartwig N-arylation of bicyclic hydrazines is described. This key reaction gives access to unique spiro[indoline-2,3'-piperidine] derivatives after reductive cleavage of the nitro-gen–nitrogen bond. This approach widens the chemical space of spirocycles and may reveal useful to explore new avenues of research in drug discovery.
Published: 2022

6. Small-Molecule 3D Ligand for RNA Recognition: Tuning Selectivity through Scaffold Hopping

Author: Simon Felder, Corinne Sagné, Erica Benedetti, and Laurent Micouin
Subjects: Small Molecule Libraries, Drug Discovery, Molecular Medicine, RNA, General Medicine, Ligands, Biochemistry
Abstract: Targeting RNAs with small molecules is considered the next frontier for drug discovery. In this context, the development of compounds capable of binding RNA structural motifs of low complexity with high affinity and selectivity would greatly expand the number of targets of potential therapeutic value. In this study, we demonstrate that tuning the three-dimensional shape of promiscuous nucleic acid binders is a valuable strategy for the design of new selective RNA ligands. Indeed, starting from a known cyanine, the simple replacement of a phenyl ring with a [2.2]paracyclophane moiety led to a new compound able to discriminate between nucleic acids showing different structural characteristics with a marked affinity and selectivity for an octahairpin loop RNA sequence. This shape modification also affected the
Published: 2022

7. Enantiopure planar chiral [2.2]paracyclophanes: Synthesis and applications in asymmetric organocatalysis

Author: Laurent Micouin, Jules Brom, Erica Benedetti, Shiqi Wu, Simon Felder, Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP)
Subjects: Planar chirality, [2.2]Paracyclophanes, 010402 general chemistry, planar chirality, 01 natural sciences, Desymmetrization, Catalysis, Analytical Chemistry, Kinetic resolution, Planar, enantioselectivity, Drug Discovery, [CHIM]Chemical Sciences, Molecule, stereoselective synthesis, ComputingMilieux_MISCELLANEOUS, Spectroscopy, Pharmacology, 010405 organic chemistry, Chemistry, asymmetric organocatalysis, Organic Chemistry, Combinatorial chemistry, 0104 chemical sciences, Enantiopure drug, Organocatalysis, Chemical stability
Abstract: This short review focuses on enantiopure planar chiral [2.2]paracyclophanes (pCps), a fascinating class of molecules that possess an unusual three-dimensional core and intriguing physicochemical properties. In the first part of the review, different synthetic strategies for preparing optically active pCps are described. Although classical resolution methods based on the synthesis and separation of diastereoisomeric products still dominate the field, recent advances involving the kinetic resolution of racemic compounds and the desymmetrization of meso derivatives open up new possibilities to access enantiopure key intermediates on synthetically useful scales. Due to their advantageous properties including high configurational and chemical stability, [2.2]paracyclophanes are increasingly employed in various research fields, ranging from stereoselective synthesis to material sciences. The applications of [2.2]paracyclophanes in asymmetric organocatalysis are described in the second part of the review. While historically enantiopure pCps have been mainly employed by organic chemists as chiral ligands in transition-metal catalysis, these compounds can also be used as efficient catalysts in metal-free reactions and may inspire the development of new transformations in the near future.
Published: 2021

8. Para‐Functionalization of N‐Substituted 4‐amino[2.2]paracyclophanes by Regioselective Formylation

Author: Laurent Micouin, Simon Felder, Erica Benedetti, Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Synthèse et structure de molécules d'interet pharmacologique (SSMIP), and Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS)
Subjects: [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Organic Chemistry, Regioselectivity, Planar chirality, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences, Formylation, Surface modification, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS
Abstract: International audience
Published: 2021

9. Bicyclic 5-5 Systems With One Bridgehead (Ring Junction) Nitrogen Atom: Two Extra Heteroatoms 2:0

Author: Erica Benedetti and Laurent Micouin
Published: 2022

10. Planar Chiral Analogues of PRODAN Based on a [2.2]Paracyclophane Scaffold: Synthesis and Photophysical Studies

Author: Simon Felder, Marie-Léonie Delcourt, Manon H. E. Bousquet, Denis Jacquemin, Rafael Rodríguez, Ludovic Favereau, Jeanne Crassous, Laurent Micouin, Erica Benedetti, Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP), Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Agence Nationale de la Recherche (ANR PhotoChiraPhane) French National Research Agency (ANR), CNRS Centre National de la Recherche Scientifique (CNRS) European Commission, Universite de Paris, Universite de Rennes 1, Universite de Nantes, Ministere de l'Enseignement Superieur et de la Recherche Estonian Research Council European Commission, Xunta de Galicia Xunta de Galicia European Commission, ANR-19-CE07-0001,PhotoChiraPhane,Synthèse et applications de catalyseurs photoredox à chiralité planaire dérivés du [2.2]paracyclophane(2019), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, [CHIM]Chemical Sciences, 010402 general chemistry, 01 natural sciences, 3. Good health, 0104 chemical sciences
Abstract: International audience; We describe the synthesis and photophysical characterization of differently substituted planar chiral analogues of PRODAN based on a [2.2]paracyclophane scaffold. This experimental and theoretical study highlights that the (chir)optical properties of the new "phane" compounds, which incorporate an electron-withdrawing propionyl moiety and an electron-donating dimethylamino group at their para or pseudo Para positions, strongly depend on their substitution patterns. In particular, for this series of molecules, a more pronounced solvatochromism and clear chiroptical behaviors are observed when the two substituents are placed on the two rings of the pCp core in a non-"co-planar" arrangement (pseudo Para derivative). This observation may help design new pCp-based luminophores with finely tuned photophysical properties.
Published: 2021

11. Revised structure of anthelvencin A and characterization of the anthelvencin biosynthetic gene cluster

Author: Laurent Micouin, Paolo Clerici, Jean-Luc Pernodet, Sylvie Lautru, Céline Aubry, Claude Gerbaud, Institut de Biologie Intégrative de la Cellule (I2BC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Microbiologie Moléculaire des Actinomycètes (ACTINO), Département Microbiologie (Dpt Microbio), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Biologie Intégrative de la Cellule (I2BC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP)
Subjects: 0301 basic medicine, Streptomyces venezuelae, Stereochemistry, [SDV]Life Sciences [q-bio], 01 natural sciences, Biochemistry, 03 medical and health sciences, Bacterial Proteins, Protein Domains, parasitic diseases, Gene cluster, medicine, Pyrroles, Anthelmintic, Peptide Synthases, biology, 010405 organic chemistry, Chemistry, General Medicine, biology.organism_classification, Streptomyces, 0104 chemical sciences, 030104 developmental biology, Multigene Family, Molecular Medicine, medicine.drug
Abstract: International audience; Anthelvencins A and B are pyrrolamide metabolites produced by Streptomyces venezuelae ATCC 14583 and 14585. Isolated in 1965, they were reported to exhibit anthelmintic and moderate antibacterial activities. In this study, we revise the structure of anthelvencin A and identify a third anthelvencin metabolite, bearing two N-methylated pyrrole groups, which we named anthelvencin C. We sequenced the genome of S. venezuelae ATCC 14583 and identified a gene cluster predicted to direct the biosynthesis of anthelvencins. Functional analysis of this gene cluster confirmed its involvement in anthelvencin biosynthesis and allowed us to propose a biosynthetic pathway for anthelvencins. In addition to a non-ribosomal peptide synthetase (NRPS), the assembly of anthelvencins involves an enzyme from the ATP-grasp ligase family, Ant23. We propose that Ant23 uses a PCP-loaded 4-aminopyrrole-2-carboxylate as substrate. As observed for the biosynthesis of the other pyrrolamides congocidine (produced by Streptomyces ambofaciens ATCC 25877) and distamycin (produced by Streptomyces netropsis DSM 40846), the NRPS assembling anthelvencins is composed of stand-alone domains only. Such NRPSs, sometimes called type II NRPSs, are less studied than the classical multimodular NRPSs. Yet, they constitute an interesting model to study protein-protein interactions in NRPSs and are good candidates for combinatorial biosynthesis approaches.
Published: 2020

12. Highly Enantioselective Asymmetric Transfer Hydrogenation: A Practical and Scalable Method To Efficiently Access Planar Chiral [2.2]Paracyclophanes

Author: Corina H. Pollok, Laurent Micouin, Simon Felder, Erica Benedetti, Serge Turcaud, Marie-Léonie Delcourt, Christian Merten, Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS)
Subjects: 010405 organic chemistry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Enantioselective synthesis, [CHIM.CATA]Chemical Sciences/Catalysis, Planar chirality, 010402 general chemistry, Transfer hydrogenation, 01 natural sciences, Desymmetrization, Combinatorial chemistry, 0104 chemical sciences, Kinetic resolution, Enantiopure drug, Planar, Molecule, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS
Abstract: We report herein a general, practical method based on asymmetric transfer hydrogenation (ATH) to control the planar chirality of a range of substituted [2.2]paracyclophanes (pCps). Our strategy enabled us to perform both the kinetic resolution (KR) of racemic compounds and the desymmetrization of centrosymmetric meso derivatives on synthetically useful scales. High selectivities (up to 99% ee) and good yields (up to 48% for the KRs and 74% for the desymmetrization reactions) could be observed for several poly-substituted paracyclophanes, including a series of bromine-containing molecules. The optimized processes could be run up to the gram scale without any loss in the reaction efficiencies. Because of its broad applicability, the ATH approach appears to be the method of choice to access planar chiral pCps in their enantiopure form.
Published: 2019

13. 3D Coumarin Systems Based on [2.2]Paracyclophane Synthesis, Spectroscopic Characterization, and Chiroptical Properties

Author: Corentin Reynaud, Laurent Micouin, Jeanne Crassous, Ludovic Favereau, Erica Benedetti, Marie-Léonie Delcourt, Serge Turcaud, Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Paris Descartes - Paris 5 (UPD5), Université Sorbonne Paris Cité (USPC), Université Paris Descartes - Faculté des Sciences Fondamentales et Biomédicales (UPD5 Sciences), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), University Paris Descartes, Ministere de l'Enseignement Superieur et de la Recherche, CNRS, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Rennes-Université de Rennes 1 (UR1), and Université de Rennes (UNIV-RENNES)
Subjects: Circular dichroism, 010405 organic chemistry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Aryl, Organic Chemistry, 010402 general chemistry, Coumarin, 01 natural sciences, Fluorescence, 3. Good health, 0104 chemical sciences, Characterization (materials science), chemistry.chemical_compound, Planar, Computational chemistry, [CHIM]Chemical Sciences, Luminescence, Visible spectrum
Abstract: International audience; In this article, we report the preparation of a series of [2.2]paracyclophane-fused coumarin systems through a simple and general procedure involving a transition-metal-catalyzed cyclization of aryl alkynoates as the key step. We also highlight the influence of the [2.2]paracyclophane (pCp) motif and its "phane" interactions on the spectroscopic properties of the newly synthesized fluorophores, which emit in the blue-green region of the visible spectrum (lambda(em), up to 560 nm) and show extremely large Stokes shifts (up to 230 nm). Finally, we demonstrate that our straightforward approach can easily be used to access optically active planar chiral 3D coumarins. Compared to previously described fluorescent paracyclophanes and other organic dyes, our compact heteroaromatic derivatives show promising chiroptical properties, both in term of circular dichroism (g(abs) similar to 8 x 10(-3)) and circularly polarized luminescence (g(lum) similar to 5 x 10(-3)), thus demonstrating a practical application of our synthetic method.
Published: 2019

14. Synthesis of Organometallic Compounds in Flow

Author: Tuan Zhao, Riccardo Piccardi, Laurent Micouin, Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP), Synthèse et structure de molécules d'interet pharmacologique (SSMIP), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), and Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS)
Subjects: 010405 organic chemistry, Chemistry, organolithium, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, organozinc, 010402 general chemistry, 01 natural sciences, Biochemistry, Combinatorial chemistry, Catalysis, 0104 chemical sciences, Inorganic Chemistry, Microreactor, Flow (mathematics), Drug Discovery, Physical and Theoretical Chemistry, organoaluminum, organomagnesium, ComputingMilieux_MISCELLANEOUS, Group 2 organometallic chemistry
Abstract: International audience; Microreactor technology has proved to be an important technique in organic synthesis, especially when organometallic compounds are used, because it allows running rapid reactions with reactive and instable intermediates. This review will highlight the preparation of main-group organometallic compounds deriving from Lithium, Magnesium, Zinc and Aluminum and their applications in flow conditions.
Published: 2019

15. Synthesis and Reactivity of Mixed Dimethylalkynylaluminum Reagents

Author: Laurent Micouin, Riccardo Piccardi, Serge Turcaud, Erica Benedetti, Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), and Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: 010405 organic chemistry, Metalation, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, 010402 general chemistry, Special class, 01 natural sciences, Combinatorial chemistry, Catalysis, 0104 chemical sciences, Alkynylation, Reagent, Electrophile, [CHIM]Chemical Sciences, Reactivity (chemistry)
Abstract: Organoaluminum derivatives are mostly appreciated for their Lewis acidity properties, but generally not considered as reagents of choice in synthetic transformations involving the creation of C–C bonds. Among these species, dimethylalkynylaluminum reagents represent a special class of compounds, with, in many cases, unique reactivity. This review summarizes the preparation and reactivity of these organometallic reagents with a focus on their synthetic potential.1 Introduction2 Preparation of Dimethylalkynylaluminum Reagents3 Reactivity of Dimethylalkynylaluminum Reagents3.1 Reactions with Csp3 Electrophiles3.2 Reactions with Csp2 Electrophiles4 Transition-Metal-Catalyzed Reactions4.1 Addition to α,β-Unsaturated Enones4.2 Coupling Reactions5 Triple Bond Reactivity6 Conclusion
Published: 2018

16. Efficient and Scalable Kinetic Resolution of Racemic 4-Formyl[2.2]paracyclophaneviaAsymmetric Transfer Hydrogenation

Author: Laurent Micouin, Erica Benedetti, Serge Turcaud, and Marie-Léonie Delcourt
Subjects: Enantiopure drug, 010405 organic chemistry, Stereochemistry, Chemistry, General Chemistry, Planar chirality, 010402 general chemistry, Transfer hydrogenation, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences, Kinetic resolution
Abstract: Herein we wish to report a new non-enzymatic kinetic resolution of racemic 4-formyl[2.2]paracyclophane based on Noyori asymmetric transfer hydrogenations (KR-ATH). Our approach, which provides an efficient access to enantiopure (Rp)- and (Sp)-4-formyl[2.2]paracyclophane (>99% ee, 39% and 41% isolated yields, respectively), is operationally simple and can be run on the gram-scale thus confirming the practical applicability of this method.
Published: 2016

17. Highly Enantioselective Desymmetrization of Centrosymmetric pseudo - para -Diformyl[2.2]paracyclophane via Asymmetric Transfer Hydrogenation

Author: Laurent Micouin, Erica Benedetti, Simon Felder, Marie-Léonie Delcourt, Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), and Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: 010405 organic chemistry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, asymmetric transfer hydrogenation, Enantioselective synthesis, chemistry.chemical_element, Regioselectivity, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, Planar chirality, 010402 general chemistry, Transfer hydrogenation, Ring (chemistry), 01 natural sciences, Desymmetrization, Combinatorial chemistry, planar chirality, Catalysis, 0104 chemical sciences, Ruthenium, desymmetrization, Enantiopure drug, centrosymmetric compounds, [CHIM]Chemical Sciences, [22]paracyclophanes
Abstract: International audience; Herein we describe the desymmetrization of a centrosymmetric pseudo-para-diformyl[2.2]paracyclophane based on Noyori asymmetric transfer hydrogenations (ATH). The reduction proceeds smoothly in the presence of commercially available ruthenium complexes to afford a monohydroxymethylated product in good yields and excellent enantioselectivities (up to 74% isolated yield and 99% ee). Our approach is operationally simple and can be run in gram-scale without any significant loss in the reaction efficiency. This desymmetrization strategy allows an easy access to an enantiopure compound bearing on each aromatic ring of the pCp core different reactive groups suitable for regioselective orthogonal postfunctionalization. T he compound [2.2]paracyclophane (pCp) and its derivatives constitute a well-known class of aromatic compounds characterized by an unusual three-dimensional framework and unique through-space interactions between their stacked aromatic subunits. 1 First discovered in the late 1940s, 2 these molecules find nowadays wide applications in material sciences for the development of through-space conjugated polymers 3 and optoelectronic devices. 4 Substituted paracyclophanes can show planar chirality due to their rigid structure which hinders the rotation of their two benzene rings. 5 This characteristic recently proved to be particularly useful for the application of pCps as chiral inductors in asymmetric catalysis and stereoselective synthesis. 1,6 Enantiopure paracyclophanes are also increasingly employed as building blocks for the development of circularly polarized light-emitting materials. 7 Over the years, optically active paracyclophanes have mostly been prepared by classical stoichiometric resolution methods and/or chromatographic separation on chiral stationary phases. 8 On the contrary, only few catalytic procedures for accessing enantioenriched pCps have been reported in the literature so far. 9 The development of new catalytic asymmetric processes allowing an efficient synthesis of planar-chiral paracyclophane derivatives is therefore highly desirable in order to expand the range of application of these molecules in different research areas. Recently, we were able to demonstrate that catalytic kinetic resolutions of racemic pCps could be employed to efficiently access valuable synthetic intermediates in their enantiopure form (Scheme 1a). 10 In order to overcome the limitation of 50% yield associated with the resolution strategy, 11 our efforts are currently directed toward the preparation of enantiopure pCp key intermediates through scalable desymmetrization reactions. The classical desymmetrization approaches involve asym-metric transformations capable of differentiating the enantio-topic functional groups of meso compounds with internal
Published: 2018

18. Diastereoselective Ring Homologation of Bicyclic Hydrazines: Access to cis -1,3-Diaminocyclohexitols

Author: Laurent Micouin, Thomas Lecourt, Aurélie Blond, Serge Turcaud, Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), 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), Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Synthèse et structure de molécules d'interet pharmacologique (SSMIP), Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC)-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), 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: Bicyclic molecule, 010405 organic chemistry, Stereochemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, General Chemical Engineering, Hydrazine, General Chemistry, 010402 general chemistry, Ring (chemistry), 01 natural sciences, 3. Good health, 0104 chemical sciences, lcsh:Chemistry, chemistry.chemical_compound, lcsh:QD1-999, chemistry, Oxidative cleavage
Abstract: International audience; A sequence of oxidative cleavage/double nitroaldol condensation followed by a few simple synthetic transformations can lead to polyhydroxylated di-and triaminocyclohexanes from a readily available bicyclic hydrazine. This new synthetic route provides a simple and general access to densely substituted privileged scaffolds or fragments with a perfect control of their relative configuration.
Published: 2018

19. Modular Access to N-Substituted cis 5-Amino-3-hydroxypiperidines

Author: Paolo Clerici, Laurent Micouin, and Paola Gordillo Guerra
Subjects: Bicyclic molecule, 010405 organic chemistry, Chemistry, Stereochemistry, Reductive cleavage, Organic Chemistry, Sequence (biology), 010402 general chemistry, Oxidative cleavage, 01 natural sciences, Reductive amination, 0104 chemical sciences, Adduct
Abstract: A sequence of oxidative cleavage/reductive amination/reductive cleavage enables the preparation of N-substituted cis 5-amino-3-hydroxypiperidines from a readily available bicyclic adduct. This new route provides straightforward and versatile access to drug-relevant scaffolds or fragments.
Published: 2017

20. Substitution of the Participating Group of Glycosyl Donors by a Halogen Atom: Influence on the Rearrangement of Transient Orthoesters Formed during Glycosylation Reactions

Author: Antoine Joosten, Vincent Gandon, Mélissa Boultadakis-Arapinis, Thomas Lecourt, Laurent Micouin, 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), Université Paris Descartes - Paris 5 (UPD5), Université Sorbonne Paris Cité (USPC), Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut de Chimie des Substances Naturelles (ICSN), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS), and Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Glycosylation, 010405 organic chemistry, Stereochemistry, Organic Chemistry, Chloroacetates, Protonation, 010402 general chemistry, 01 natural sciences, Acceptor, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Group (periodic table), Halogen, Atom, [CHIM]Chemical Sciences, Glycosyl
Abstract: International audience; Substitution of the participating group of glycosyl donors by a halogen atom is shown to specifically induce degradation of transient orthoesters formed during glycosylation reactions, depending on the nature of the acceptor, and to affect the protonation profile of those intermediates. Following these findings, bromo- and chloroacetates, which are major protecting groups in glycochemistry because they are orthogonal to other esters, should be considered with care as participating groups in the future.
Published: 2017

21. Synthesis and photophysical studies of through-space conjugated [2.2]paracyclophane-based naphthalene fluorophores

Author: Marie-Léonie Delcourt, B. Gatin-Fraudet, Laurent Micouin, Erica Benedetti, Serge Turcaud, Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), and Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: 010405 organic chemistry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, General Chemical Engineering, General Chemistry, Conjugated system, 010402 general chemistry, Photochemistry, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Intramolecular force, [CHIM]Chemical Sciences, Naphthalene
Abstract: International audience; In this work we report a straightforward method for the synthesis of a new class of small organic fluorophores bearing both [2.2]paracyclophane and naphthalene subunits using an intramolecular dehydrogenative Diels-Alder reaction as a key step. These compounds are characterized by a compact three-dimensional structure as well as through-space conjugated push-pull systems, and possess interesting spectroscopic characteristics that may be useful for the development of innovative chemical probes and optical sensors. Since the discovery of their parent compound in 1949, 1 mono-and polysubstituted [2.2]paracyclophane derivatives (pCp) have attracted increasing attention within the scientic community and have become the object of many studies in the last few decades. Initial investigations on the synthesis and derivatization of [2.2]paracyclophanes mainly aimed at disclosing the unusual reactivity of these molecules. 2 More recently, functionalized pCps have emerged as powerful ligands or auxiliaries in asym-metric catalysis and stereoselective synthesis. 3 Substituted paracyclophanes also found applications in material sciences as monomers for the synthesis of through-space conjugated polymers , 4 or for the production of functionalized surfaces using chemical vapor deposition (CVD) methods. 5 Due to their uncommon electronic structure, [2.2] paracyclophanes display intrinsic uorescence and can be employed to access new organic dyes. Accordingly, a wide range of pCp-based stilbene uorophores have been reported in the literature over the past few years. 6 These molecules typically present a "branched" p-extended three-dimensional structure functionalized with differently substituted para-phenylene vinylene subunits (Fig. 1a). The pCp-based stilbene uo-rophores, whose photophysical properties are generally tuned by introducing electron-donating or electron-withdrawing groups on their alkene moieties, revealed to be particularly useful in solid state application for the development of organic light-emitting diodes (OLEDs), 7 and non-linear optical materials. 8 A different approach to modulate the spectroscopic characteristics of the pCp-based uorophores consists in expanding the benzene rings of [2.2]paracyclophane to functionalized poly-condensed aromatic hydrocarbons. This should lead to more compact dyes potentially useful for the design of innovative chemical probes and biosensors. Surprisingly, this approach has only been scarcely investigated up to now. 9 In this context, our group recently became interested in the possibility to incorporate naphthalene p-conjugated frameworks (Fig. 1b) into one of the aromatic decks of pCp to tune their photophysical properties. 10 We therefore decided to focus our attention on the elaboration of pCp-based naphthalene frameworks (Fig. 1c) by an intramolecular dehydrogenative-Diels-Alder (DDA) reaction. This strategy was reported to be particularly versatile for the synthesis of tunable sol-vatochromic uorophores, 11 but has never been described on pCp. The DDA precursors 4a-h were prepared in three steps starting from differently substituted 4-formyl-[2.2] Fig. 1 (a) Structure of pCp-based stilbene fluorophores. (b) General structure of two-dimensional naphthalene systems. (c) Structure of pCp-based naphthalene fluorophores.
Published: 2017

22. Use of a redox probe for an electrochemical RNA–ligand binding assay in microliter droplets

Author: François Mavré, Benoît Limoges, Laurent Micouin, Hélène Guyon, Marjorie Catala, Franck Brachet, Carine Tisné, Serge Turcaud, Laboratoire d'Electrochimie Moléculaire (LEM (UMR_7591)), Université Paris Diderot - Paris 7 (UPD7)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Morphogénèse du Cerveau des Vertébrés = Morphogenesis of the vertebrate brain (LBD-E10), Laboratoire de Biologie du Développement (LBD), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Biologie Paris Seine (IBPS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Biologie Paris Seine (IBPS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM), Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de cristallographie et RMN biologiques (LCRB - UMR 8015), Université Paris Diderot - Paris 7 (UPD7)-Centre National de la Recherche Scientifique (CNRS), Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Biologie Paris Seine (IBPS), Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), and Centre National de la Recherche Scientifique (CNRS)-Université Paris Descartes - Paris 5 (UPD5)
Subjects: 0301 basic medicine, Surface Properties, Analytical chemistry, Ligands, Electrochemistry, Redox, Catalysis, Electrochemical cell, Small Molecule Libraries, 03 medical and health sciences, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Materials Chemistry, Electroanalytical method, Particle Size, Binding Sites, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Ligand binding assay, Metals and Alloys, RNA, Electrochemical Techniques, General Chemistry, Aptamers, Nucleotide, Combinatorial chemistry, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, [SDV.BBM.BP]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biophysics, 030104 developmental biology, Ceramics and Composites, Oxidation-Reduction
Abstract: International audience; In this work, we report an affordable, sensitive, fast and user-friendly electroanalytical method for monitoring the binding between unlabeled RNA and small compounds in microliter-size droplets using a redox-probe and disposable miniaturized screen-printed electrochemical cells. Increasing evidence has shown that non-coding RNAs play a key role in many biological functions and are involved not only in infectious but also in many other human diseases. 1 Despite an exploding number of biological studies suggesting RNA-regulated pathways as potential drug targets, the design of small, drug-like compounds able to selectively bind and modulate RNA functions is still difficult. 2 This is quite surprising if one considers that interaction with ribosomal RNA is one of the major modes of action of antibiotics 3 and that small metabolites are known to regulate basic functions of prokaryotes by interacting with riboswitches. 4
Published: 2017

23. Functionalization of the Anomeric C–H Bond of Carbohydrates: Old Strategies and New Opportunities

Author: Mélissa Boultadakis-Arapinis, Laurent Micouin, Thomas Lecourt, and Camille Lescot
Subjects: chemistry.chemical_compound, Glycosylation, Anomer, chemistry, Stereochemistry, Organic Chemistry, Surface modification, Stereoselectivity, Diazo, Carbene, Acceptor, Catalysis
Abstract: After a quick review of the existing methods that enable the quaternarization of the anomeric position of carbohydrates via a C–H bond functionalization process, we summarize recent contributions from our group related to the preparation of α- and β-ketopyranosides by the 1,5-insertion of metal carbenes. 1 Introduction 2 Early Developments: Anchoring of Reactive Species at the Anomeric Position 2.1 Radical-Promoted Quaternarization of the Anomeric Position 2.2 Photochemically Induced Quaternarization of the Anomeric Position 2.3 Alkylidene-Promoted Quaternarization of the Anomeric Position 2.4 Nitrene-Promoted Quaternarization of the Anomeric Position 2.5 Any Possible Extension to the Preparation of α- and β-Ketopyranosides? 3 Carbene-Mediated Functionalization of the Anomeric C–H Bond of Carbohydrates 3.1 Functionalization of Carbohydrate Scaffolds by the Insertion of Metal Carbenes: A Challenging Task 3.2 Preparation of Carbene Precursors 3.3 Transition Metal Catalyzed Decomposition of Diazo Sugars 3.4 Dramatic Effects of Molecular Sieves 3.5 Ring Opening of γ-Lactones 4 Development of a Stereoselective Glycosylation/Diazo Transfer/Quaternarization Sequence 4.1 Preliminary Studies with a Permethylated Acceptor 4.2 Stereoselective Access to Quaternary Disaccharides: Scope and Limitations 5 Concluding Remarks
Published: 2013

24. Continuous Flow Synthesis of Dimethylalkynylaluminum Reagents

Author: Riccardo Piccardi, Laurent Micouin, Anais Coffinet, Serge Turcaud, Erica Benedetti, Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS)
Subjects: 010405 organic chemistry, Chemistry, Metalation, Continuous flow, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Flow chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Flow conditions, Scientific method, Reagent, Organic chemistry, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS
Abstract: A new process for the synthesis of dimethylalkynylaluminum reagents under flow conditions is described. It involves a base-catalyzed alumination of terminal alkynes using a resin-supported organocatalyst. Final organometallic species are obtained in solution, and can further react with various aldehydes or nitrones.
Published: 2016

25. ChemInform Abstract: Efficient and Scalable Kinetic Resolution of Racemic 4-Formyl[2.2]paracyclophane via Asymmetric Transfer Hydrogenation

Author: Erica Benedetti, Marie-Léonie Delcourt, Laurent Micouin, and Serge Turcaud
Subjects: Enantiopure drug, Computational chemistry, Chemistry, Scalability, General Medicine, Transfer hydrogenation, Kinetic resolution
Abstract: Herein we wish to report a new non-enzymatic kinetic resolution of racemic 4-formyl[2.2]paracyclophane based on Noyori asymmetric transfer hydrogenations (KR-ATH). Our approach, which provides an efficient access to enantiopure (Rp)- and (Sp)-4-formyl[2.2]paracyclophane (>99% ee, 39% and 41% isolated yields, respectively), is operationally simple and can be run on the gram-scale thus confirming the practical applicability of this method.
Published: 2016

26. Rhodium(II)-Alkynyl Carbenoids Insertion into Si–H bonds: An Entry to Propargylic Geminal Bis(silanes)

Author: Serge Turcaud, Rahul Kumar, Thibaut Courant, Laurent Micouin, 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), Service de Chimie Bio-Organique et de Marquage (SCBM), Médicaments et Technologies pour la Santé (MTS), Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Synthèse et structure de molécules d'interet pharmacologique (SSMIP), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), 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: Silanes, Geminal, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Biochemistry, 3. Good health, 0104 chemical sciences, Rhodium, chemistry.chemical_compound, chemistry, Polymer chemistry, Organic chemistry, Reactivity (chemistry), Physical and Theoretical Chemistry
Abstract: International audience; α-Alkynyl-α′-trimethylsilylhydrazones are used as novel Rh(II)-carbenoids precursors. These new carbenoids have shown very good reactivity in Si−H insertion reactions, leading to original propargylic geminal-bis(silanes) in a two-step sequential process.
Published: 2016

27. The Chemistry of Alkynylaluminum Species

Author: Laurent Micouin, Riccardo Piccardi, Olivier Jackowski, Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Réactivité organométallique et catalyse pour la synthèse (ROCS), Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Marek, Ilan
Subjects: trimethylaluminum, 010405 organic chemistry, Chemistry, alanates, POLE 1, 010402 general chemistry, 01 natural sciences, ROCS, 3. Good health, 0104 chemical sciences, alanes, Environmental chemistry, [CHIM]Chemical Sciences, Chemistry (relationship), acetylides, alkynylaluminum, Lewis acidity, triethylaluminum
Abstract: International audience; Among organoaluminum reagents, alkynylaluminum species exhibit peculiar physicochemical properties and reactivity. Depending on the nature of easily controlled parameters such as substituents on the aluminum center or additives and solvent, their Lewis acidity and nucleophilicity can be independently fine-tuned in a very precise manner. This chapter describes the preparation of alkynylaluminum compounds, their structure, and their reactivity in several synthetic transformations involving the transfer of their alkynyl group such as nucleophilic substitution reactions, additions to C\textendash X multiple bonds, epoxide and aziridine ring-opening reactions, reactions with oxonium and iminium species, metal-assisted cross-coupling reactions, as well as in rearrangements. The reactivity of the triple bond of these reagents is also presented.
Published: 2016

28. Gram-Scale Quaternarization of the Anomeric Position of Carbohydrates: Dramatic Effects of Molecular Sieves on Rhodium(II)-Mediated Decomposition of Diazo Sugars

Author: Camille Lescot, Laurent Micouin, Mélissa Boultadakis-Arapinis, and Thomas Lecourt
Subjects: Anomer, Chemistry, Organic Chemistry, Substrate (chemistry), chemistry.chemical_element, Molecular sieve, Catalysis, Rhodium, chemistry.chemical_compound, Surface modification, Organic chemistry, Diazo, Carbene
Abstract: The optimization of rhodium(II) carbene mediated quaternarization of the anomeric position of carbohydrates is reported. Preparation of ketopyranosides in good and reliable yields requires reverse addition of the substrate to a highly diluted suspension of the catalyst in refluxing 1,2-dichloroethane, as well as addition of a carefully controlled amount of molecular sieves, and vigorous stirring. Following these optimized reaction conditions, functionalization of the anomeric position of carbohydrates can finally be performed on a preparative scale.
Published: 2012

29. Rh(II) Carbene-Mediated Synthesis of Methyl α- and β-Ketopyranosides: Preparation of Carbene Precursors, Quaternarization of the Anomeric Position, and Ring Opening of γ-Lactones

Author: Camille Lescot, Laurent Micouin, Mélissa Boultadakis-Arapinis, and Thomas Lecourt
Subjects: chemistry.chemical_compound, Anomer, Stereochemistry, Chemistry, Organic Chemistry, Surface modification, Ring (chemistry), Biochemistry, Carbene, Catalysis
Abstract: Methyl α- and β-ketopyranosides were efficiently prepared by carbene-mediated quaternarization of the anomeric position of corresponding aldopyranosides. Preparation of carbene precursors proved to be tedious and required a two-step procedure involving first bromoacetylation, followed by diazo-transfer with N,N′-ditosylhydrazine and DBU. Selective functionalization of the anomeric C-H bond was then achieved under Rh2(OAc)4 or Rh2(acam)4 catalysis. Finally, ring opening of the resulting γ-lactones delivered α- and β-ketopyranosides with the anomeric position functionalized by an independent chain.
Published: 2011

30. Chemodivergent Synthesis of 7-Aryl/alkyl-6-hydroxy-1,4-oxazepan-5-ones and 2-[Aryl/alkyl(hydroxy)methyl]morpholin-3-ones from a Common Epoxyamide Precursor

Author: David M. Aparicio, Jorge R. Juárez, Laurent Micouin, Joel L. Terán, Marcos Flores-Alamo, Dino Gnecco, Angel Mendoza, Luis F. Roa, and María L. Orea
Subjects: chemistry.chemical_classification, medicine.drug_class, Aryl, Organic Chemistry, Diastereomer, Epoxide, Carboxamide, Medicinal chemistry, Chemical synthesis, Catalysis, chemistry.chemical_compound, chemistry, Alkoxide, medicine, Chemoselectivity, Alkyl
Abstract: We present here a regiospecific synthesis of 7-alkyl- or 7-aryl-6-hydroxy-1,4-oxazepan-5-ones and 2-[aryl(hydroxy)methyl]- or 2-(1-hydroxyalkyl)morpholin-3-ones from a diastereomeric mixture of trans-3-alkyl- or -3-aryl-N-(2-hydroxyethyl)-N-(1-phenylethyl)oxirane-2-carboxamides. This chemodivergent synthesis is easily controlled by an appropriate choice of cyclization reaction conditions.
Published: 2011

31. Direct Synthesis of 1,4-Disubstituted-5-alumino-1,2,3-triazoles: Copper-Catalyzed Cycloaddition of Organic Azides and Mixed Aluminum Acetylides

Author: Laurent Micouin, Thomas Lecourt, Yuhan Zhou, Synthèse et structure de molécules d'interet pharmacologique (SSMIP), and Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Azides, chemistry.chemical_element, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, Aluminium, Organic chemistry, Molecule, Molecular Structure, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Regioselectivity, General Chemistry, General Medicine, Triazoles, Combinatorial chemistry, Copper, Cycloaddition, 0104 chemical sciences, chemistry, Electrophile, Solvents, Click chemistry, Aluminum
Abstract: International audience; Aluminotriazoles are obtained in a fully chemo‐ and regioselective manner by a copper‐catalyzed cycloaddition of organic azides with mixed‐aluminum acetylides (see scheme). The carbon-aluminum bond, which is unaffected by the first transformation, is still able to react further with different electrophiles.
Published: 2010

32. Room Temperature Lewis Base-Catalyzed Alumination of Terminal Alkynes

Author: Laurent Micouin, Thomas Lecourt, and Yuhan Zhou
Subjects: chemistry.chemical_compound, Terminal (electronics), Trimethylsilyl, chemistry, Metalation, Methylamine, Reagent, Organic chemistry, General Chemistry, Lewis acids and bases, Catalysis
Abstract: An efficient and mild access to mixed dimethylalkynylaluminum reagents has been developed via a direct Lewis base-catalyzed alumination of terminal alkynes by trimethylaluminum. The use of bis(trimethylsilyl)methylamine enables the metalation at room temperature with only 1% of catalyst loading.
Published: 2009

33. Focus on the Controversial Activation of Human iNKT Cells by 4-Deoxy Analogue of KRN7000

Author: Virginie Blot, Julie Hunault, Jacques Le Pendu, Didier Dubreuil, Anne-Laure Turcot-Dubois, Laurent Micouin, Marc Bonneville, Vivien Lacone, Thomas Lecourt, Séverine Marionneau, Jézabelle Rocher, Muriel Pipelier, Monique Clément, and J.Y. Douillard
Subjects: Galactosylceramides, Stimulation, Lymphocyte Activation, Natural killer cell, Interferon-gamma, Mice, Structure-Activity Relationship, chemistry.chemical_compound, Glycolipid, Adjuvants, Immunologic, In vivo, Drug Discovery, medicine, Animals, Humans, Sphingosine, Tumor Necrosis Factor-alpha, Chemistry, Biological activity, Sphingolipid, In vitro, Cell biology, medicine.anatomical_structure, Biochemistry, Natural Killer T-Cells, Molecular Medicine, Interleukin-4
Abstract: 4-Deoxy-alpha-GalCer analogues are considered weaker agonists than KRN7000 for the stimulation of human iNKT cells, but this remains strongly debated. In this work, we described a strategy toward 4-deoxy-alpha-GalCers with, as a key step, a metathesis reaction allowing sphingosine modifications from a single ethylenic alpha-galactoside precursor. The 4-deoxy-KRN7000 derivative 2, described here, induced potent cytokinic responses, comparable to those of KRN7000, both from human iNKT cells in vitro and from their murine counterpart in vivo.
Published: 2009

34. NMR-Guided Fragment-Based Approach for the Design of AAC(6′)-Ib Ligands

Author: Frédérique Maurice, Laurent Micouin, Frédéric Dardel, Serge Turcaud, Thomas Lecourt, Thomas Lombès, Guillaume Begis, Synthèse et structure de molécules d'interet pharmacologique (SSMIP), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de cristallographie et RMN biologiques (LCRB - UMR 8015), Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), 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 National de la Recherche Scientifique (CNRS)-Université Paris Descartes - Paris 5 (UPD5), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), and Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Binding Sites, Magnetic Resonance Spectroscopy, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Stereochemistry, Organic Chemistry, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, Nuclear magnetic resonance spectroscopy, Ligands, 010402 general chemistry, 01 natural sciences, Biochemistry, Combinatorial chemistry, 0104 chemical sciences, 3. Good health, Aminoglycosides, Fragment (logic), Acetyltransferases, Drug Design, Molecular Medicine, Enzyme Inhibitors, Binding site, Molecular Biology, Protein Binding
Abstract: International audience; Ligand‐observed NMR experiments have been used to drive the detection and optimisation of non‐aminoglycosidic ligands for AAC(6′)Ib, one of the most clinically important resistance enzymes to aminoglycosides. This fragment‐based approach has been conducted without any need for NMR structural assignment of the target, and has been validated by the preparation of a bisubstrate inhibitor.
Published: 2008

35. Monitoring of reversible boronic acid-diol interactions by fluorine NMR spectroscopy in aqueous media

Author: Mélanie Etheve-Quelquejeu, Laurent Micouin, Marjorie Catala, Laura Iannazzo, Erica Benedetti, and Carine Tisné
Subjects: inorganic chemicals, Aqueous medium, Organic Chemistry, Diol, Fluorine-19 NMR, Nuclear magnetic resonance spectroscopy, Bioinformatics, Biochemistry, Combinatorial chemistry, chemistry.chemical_compound, chemistry, Physical and Theoretical Chemistry, Spectroscopy, Boronic acid
Abstract: Recognition and sensing of various biologically relevant species using boronic acid-based chemosensors have become increasingly popular over the last few years. Herein, we describe a new convenient method for monitoring boronic acid-diol interactions in aqueous media based on (19)F NMR spectroscopy with fluorinated boronic acid probes.
Published: 2015

36. ChemInform Abstract: The Reaction of Dimethylalkynylaluminum Reagents with Trimethylsilyldiazomethane: Original Reactivity Leading to New α-Silylated Alkynyl Hydrazones

Author: Laurent Micouin, Rahul Kumar, and Serge Turcaud
Subjects: chemistry.chemical_compound, Trimethylsilyl, Chemistry, Diazomethane, Reagent, Organic chemistry, Reactivity (chemistry), General Medicine, Trimethylsilyldiazomethane
Abstract: Various α-silylated alkynylhydrazones are prepared by the reaction of substituted alkynylaluminium compounds with trimethylsilyl diazomethane (II).
Published: 2015

37. Asymmetric 1,3-dipolar cycloadditions of a chiral nonracemic glyoxylic azomethine imine

Author: Martine Bonin, Laurent Micouin, Florence Chung, Ariane Chauveau, and Mohamed Seltki
Subjects: chemistry.chemical_classification, Stereochemistry, Organic Chemistry, Imine, Substituent, Enantioselective synthesis, Biochemistry, Medicinal chemistry, Styrene, chemistry.chemical_compound, chemistry, Ylide, Drug Discovery, Reactivity (chemistry), Stereoselectivity, Selectivity
Abstract: The reactivity of a chiral nonracemic glyoxylic azomethine imine has been investigated. This species reacts with a wide range of dipolarophiles, with a complete regio- and facial stereoselectivity. The introduction of an electron-withdrawing substituent on the ylide leads to a lower endo selectivity with electron-withdrawing dipolarophiles, but to an improved exo selectivity with styrene derivatives when compared to the reactivity of aliphatic- or aromatic-substituted ylides.
Published: 2004

38. Practical Asymmetric Synthesis of 1,2-Diamines in the 3-Aminoazepane Series

Author: Laurent Micouin, Sabrina Cutri, Henri-Philippe Husson, Martine Bonin, Angèle Chiaroni, Institut de Chimie des Substances Naturelles (ICSN), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Département Territoires, Environnement et Acteurs (Cirad-TERA), Centre de Coopération Internationale en Recherche Agronomique pour le Développement (Cirad), Synthèse et structure de molécules d'interet pharmacologique (SSMIP), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS), and Département Territoires, Environnement et Acteurs (TERA)
Subjects: Tandem, Bicyclic molecule, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Organic Chemistry, Enantioselective synthesis, General Medicine, Alkylation, 010402 general chemistry, 01 natural sciences, Chemical synthesis, Combinatorial chemistry, 0104 chemical sciences, chemistry.chemical_compound, Azepane, Diamine, Aminal, Organic chemistry
Abstract: International audience; A simple and versatile method for the enantio-and diastereoselective synthesis of mono-or disubstituted 3-aminoazepanes is described. The key step involves a highly regio-and diastereoselective tandem ring-enlargement/alkylation or reduction process. This novel synthetic route provides enantiomerically pure constrained diamines interesting as scaffolds for medicinal chemistry.
Published: 2003

39. The reaction of dimethylalkynylaluminum reagents with trimethylsilyldiazomethane: original reactivity leading to new α-silylated alkynyl hydrazones

Author: Laurent Micouin, Rahul Kumar, Serge Turcaud, Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), and Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Trimethylsilyl Compounds, Trimethylsilyl, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, chemistry.chemical_compound, Organometallic Compounds, Organic chemistry, Reactivity (chemistry), Physical and Theoretical Chemistry, Molecular Structure, 010405 organic chemistry, Diazomethane, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Hydrazones, Stereoisomerism, Silanes, Combinatorial chemistry, 0104 chemical sciences, chemistry, Reagent, Alkynes, Indicators and Reagents, Trimethylsilyldiazomethane, Aluminum
Abstract: International audience; Trimethylsilyl (TMS) diazomethane does not react as a homologating reagent but as a C-electrophilic species with dimethylalkynylaluminum reagents. This unprecedented reactivity enables a simple access to unusual α-silylated alkynyl hydrazones.
Published: 2014

40. The design of RNA binders: targeting the HIV replication cycle as a case study

Author: Laurent Micouin, Carine Tisné, Aurélie Blond, and Eric Ennifar
Subjects: Models, Molecular, Anti-HIV Agents, Human immunodeficiency virus (HIV), Computational biology, Biology, medicine.disease_cause, Biochemistry, Antiviral Agents, Transactivation, Transcription (biology), Drug Discovery, medicine, Animals, Humans, General Pharmacology, Toxicology and Pharmaceutics, Nuclear export signal, Pharmacology, Genetics, Organic Chemistry, RNA, Replication cycle, Reverse transcriptase, In vitro, Drug Design, Molecular Medicine, RNA, Viral
Abstract: The human immunodeficiency virus 1 (HIV-1) replication cycle is finely tuned with many important steps involving RNA-RNA or protein-RNA interactions, all of them being potential targets for the development of new antiviral compounds. This cycle can also be considered as a good benchmark for the evaluation of early-stage strategies aiming at designing drugs that bind to RNA, with the possibility to correlate in vitro activities with antiviral properties. In this review, we highlight different approaches developed to interfere with four important steps of the HIV-1 replication cycle: the early stage of reverse transcription, the transactivation of viral transcription, the nuclear export of partially spliced transcripts and the dimerization step.
Published: 2014

41. ChemInform Abstract: Modular Access to N-Substituted cis-3,5-Diaminopiperidines

Author: Paul Dockerty, Aurelie Blond, Serge Turcaud, Raquel Álvarez, Laurent Micouin, and Thomas Lecourt
Subjects: chemistry.chemical_classification, Bicyclic molecule, business.industry, Hydrazine, Sequence (biology), General Medicine, Modular design, Reductive amination, Combinatorial chemistry, chemistry.chemical_compound, chemistry, Hydrogenolysis, Bridged compounds, business, Oxidative cleavage
Abstract: A sequence of oxidative cleavage/reductive amination/hydrogenolysis enables the preparation of N-substituted cis-3,5-diaminopiperidines from a readily available bicyclic hydrazine. This new synthetic route provides a simple and general access to RNA-friendly fragments with a good chemical diversity.
Published: 2014

42. Electronic Effects in Carbene-Mediated C H Bond Functionalization: An Experimental and Theoretical Study

Author: Laurent Micouin, Mélissa Boultadakis-Arapinis, Elise Prost, Vincent Gandon, Thomas Lecourt, Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Génie Enzymatique et Cellulaire (GEC), Université de Technologie de Compiègne (UTC)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS), 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), Synthèse et structure de molécules d'interet pharmacologique (SSMIP), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie des Substances Naturelles (ICSN), Centre National de la Recherche Scientifique (CNRS), Transformation Intégrée de la Matière Renouvelable (TIMR), Université de Technologie de Compiègne (UTC), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Synthèse et structure de molécules d'interet pharmacologique ( SSMIP ), Université Paris Descartes - Paris 5 ( UPD5 ) -Centre National de la Recherche Scientifique ( CNRS ), Institut de Chimie des Substances Naturelles ( ICSN ), Centre National de la Recherche Scientifique ( CNRS ), Transformation Intégrée de la Matière Renouvelable ( TIMR ), Université de Technologie de Compiègne ( UTC ), Chimie Organique et Bioorganique : Reactivité 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 ), Normandie Université ( NU ) -Centre National de la Recherche Scientifique ( CNRS ) -Université de Rouen Normandie ( UNIROUEN ), and Normandie Université ( NU ) -Centre National de la Recherche Scientifique ( CNRS )
Subjects: Concerted reaction, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Heteroatom, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, Photochemistry, [ CHIM.CATA ] Chemical Sciences/Catalysis, chemistry.chemical_compound, [ CHIM.ORGA ] Chemical Sciences/Organic chemistry, Computational chemistry, Electrophile, Electronic effect, Reactivity (chemistry), Lone pair, Isomerization, Carbene, ComputingMilieux_MISCELLANEOUS
Abstract: International audience; In this article, we show that short-distance and long-range electronic effects are strongly affecting the mechanism and stereoselectivity of Rh(II)-carbene mediated C-H functionalization processes. Based on experimental studies with deuterium-labelled carbohydrates and DFT calculations, we show that the orientation of the lone pairs of adjacent heteroatoms, as well as the nature of substituents located far from the reaction center, are inducing a shift from the classical concerted mechanism to the less common stepwise process. Furthermore, we reveal that the stereochemical outcome of these transformations is depending on the relative energies of the C-H bond activation and Rh(II)-carbene isomerization barriers. The formation of a single diastereoisomer is thus resulting from Curtin–Hammet-like kinetics when insertion occurs in poorly activated C-H bonds. However, the formation of diastereoisomeric mixtures is resulting from two disconnected and totally stereoselective transformations when the reactivity of the C-H bonds towards electrophilic metallocarbenes is increased by short-distance or long-range electronic effects.
Published: 2014

43. Asymmetric functionalization of a chiral non-racemic oxazolidine ester enolate. A new route towards the preparation of quaternary serine esters

Author: Claude Riche, Angèle Chiaroni, Laurent Micouin, Valérie Alezra, Martine Bonin, and Henri-Philippe Husson
Subjects: Serine, Oxazolidine, chemistry.chemical_compound, chemistry, Stereochemistry, organic chemicals, Organic Chemistry, Drug Discovery, polycyclic compounds, Surface modification, heterocyclic compounds, Biochemistry
Abstract: A new route towards the preparation of enantiomerically pure quaternary serine esters is described. The key step involves the diastereoselective functionalization of an oxazolidine ester enolate having an exocyclic chiral appendage.
Published: 2000

44. Diastereoselective synthesis of 2-aryl-3-aminoazepanes via a novel ring-enlargement process

Author: Olivier Froelich, Jean-Charles Quirion, Sabrina Cutri, Laurent Micouin, Martine Bonin, and Henri-Philippe Husson
Subjects: chemistry.chemical_compound, chemistry, Aryl, Organic Chemistry, Drug Discovery, Stereoselectivity, Ring (chemistry), Biochemistry, Combinatorial chemistry
Abstract: Syntheses of optically pure 2-aryl-3-aminoazepanes derived from 2-cyano 6-oxazolopiperidine are described. The key step involves a one-pot reduction and ring-enlargement process occurring in a highly regio- and stereoselective way.
Published: 2000

45. Fast ester cleavage of sterically hindered α- and β-aminoesters under non-aqueous conditions. Application to the kinetic resolution of aziridine esters

Author: Laurent Micouin, Martine Bonin, Celine Bouchet, Valérie Alezra, and Henri-Philippe Husson
Subjects: Steric effects, chemistry.chemical_compound, Aqueous solution, Chemistry, Organic Chemistry, Drug Discovery, Chelation, Cleavage (crystal), Aziridine, Biochemistry, Medicinal chemistry, Kinetic resolution
Abstract: Various protected α- and β-aminoesters undergo fast ester cleavage by treatment with t -BuOK in THF. The accelerating effect of a neighboring chelating group was used for the efficient kinetic resolution of non-racemic aziridine esters.
Published: 2000

46. Practical preparation and substitution of configurationally stable aziridinyl ester anions

Author: Henri-Philippe Husson, Laurent Micouin, Martine Bonin, and Valérie Alezra
Subjects: chemistry.chemical_compound, law, Chemistry, Organic Chemistry, Drug Discovery, Substitution (logic), Electrophile, Organic chemistry, Carboxylate, Aziridine, Biochemistry, Walden inversion, law.invention
Abstract: Configurationally and chemically stable aziridine carboxylate anions have been generated. These intermediates are stable at −78°C for several hours and react with electrophiles with good to excellent retention of configuration.
Published: 2000

47. Diastereoselective Cycloadditions of Chiral Non-racemic Azomethine Imines

Author: Fanny Roussi, Laurent Micouin, Martine Bonin, Henri-Philippe Husson, and Ariane Chauveau
Subjects: Chemistry, Stereochemistry, Organic Chemistry, Enantioselective synthesis, Catalysis
Published: 2000

48. Asymmetric 1,3-dipolar cycloadditions of a chiral non-racemic azomethine imine

Author: Claude Riche, Angèle Chiaroni, Laurent Micouin, Fanny Roussi, Martine Bonin, and Henri-Philippe Husson
Subjects: Benzaldehyde, chemistry.chemical_compound, Dipole, Chemistry, Stereochemistry, Organic Chemistry, Drug Discovery, Imine, Biochemistry
Abstract: Chiral non racemic carbazate 1, derived from (R)-(−)-phenylglycinol, reacts regioselectively with benzaldehyde or its dimethylacetal to give an azomethine imine. The facial, endo exo and regio selectivities of 1,3-dipolar cycloadditions of this reactive species with various dipolarophiles have been studied and are described in this paper. In the best cases, up to three contiguous asymmetric centers could be generated simultaneously, in a complete enantio- and diastereoselective fashion.
Published: 1999

49. Asymmetric Routes Towards Polyfunctionalized Pyrrolidines: A Short Diastereoselective Synthesis of Polyhydroxylated Pyrrolidines and an Indolizidine

Author: Bruno Dudot, Jacques Royer, Isabelle Baussanne, and Laurent Micouin
Subjects: chemistry.chemical_compound, chemistry, Stereochemistry, Organic Chemistry, Indolizidine, Aldol condensation, Catalysis, 8-epi-swainsonine
Published: 1999

50. Diastereoselective alkynylation of chiral non-racemic oxazolidines with mixed organoaluminum compounds

Author: Angèle Chiaroni, Martine Bonin, Jérôme Blanchet, Laurent Micouin, Henri-Philippe Husson, Claude Riche, Université Paris Descartes - Paris 5 (UPD5), Synthèse et structure de molécules d'interet pharmacologique (SSMIP), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie des Substances Naturelles (ICSN), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques (LCBPT - UMR 8601), Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Centre National de la Recherche Scientifique (CNRS)
Subjects: Alkynylation, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Reagent, Organic Chemistry, Drug Discovery, 010402 general chemistry, 01 natural sciences, Biochemistry, Combinatorial chemistry, ComputingMilieux_MISCELLANEOUS, 0104 chemical sciences
Abstract: A new efficient and scalable route to chiral non-racemic α-substituted propargylamines is described. The reaction pathway consists of the diastereoselective addition of mixed alkynylaluminum reagents to oxazolidines derived from R-(−)-phenylglycinol.
Published: 1999

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