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159 results on '"Vincent Gandon"'

4. Expedient Access to Polyaromatic Biaryls by Unconventional Ag-Catalyzed Cycloaromatization of Alkynylthiophenes and Au-Catalyzed Double C–H Activation

Author

Rakesh K. Saunthwal, Kapil Mohan Saini, Nicolas Grimblat, Abhinandan K. Danodia, Sushil Kumar, Vincent Gandon, and Akhilesh K. Verma

Subjects
Cyclization, Organic Chemistry, Physical and Theoretical Chemistry, Biochemistry, Catalysis
Abstract

An unconventional approach for the regioselective synthesis of polyaromatic biaryls via site-selective Ag-catalyzed twofold electrophilic cycloisomerization followed by Au-catalyzed double C-H activation is described. The developed process allows the synthesis of highly decorated biaryls with excellent regioselectivity. As revealed by DFT computations, the reaction represents a rare example of C1-C5

Published
2022

5. Palladium-Catalyzed Regioselective Arylalkenylation of Ynamides

Author

Rajeshwer Vanjari, Shubham Dutta, Shengwen Yang, Vincent Gandon, and Akhila K. Sahoo

Subjects
Organic Chemistry, Physical and Theoretical Chemistry, Biochemistry
Abstract

A cationic palladium-catalyzed arylalkenylation of ynamides is presented. The putative keteniminium arylpalladium intermediate likely dictates the regioselective carbopalladation of the ynamide to form a vinylpalladium species. The capture of this complex by the olefin yields linear conjugated β-alkenyl aminodienes (especially with

Published
2022

6. Leveraging the Domino Skeletal Expansion of Thia-/Selenazolidinones via Nitrogen-Atom Transfer in Hexafluoroisopropanol: Room Temperature Access to Six-Membered S/Se,N-Heterocycles

Author

Vandana Jaiswal, Mangilal Godara, Dinabandhu Das, Vincent Gandon, and Jaideep Saha

Subjects
Hydrocarbons, Fluorinated, Nitrogen, Propanols, Organic Chemistry, Temperature, Catalysis
Abstract

Herein, a highly regioselective domino skeletal-expansion process that transforms 2-aminothiazolidinone into six-membered S,N-heterocycle is developed with the aid of TMS-azide in hexafluoroisopropanol (HFIP) at ambient temperature. Functioning of the C2 tertiary amine as latent reactive group on thiazolidinone moiety was the key to this development, which allowed relay substitution with azide and imparted subsequent ring-expansion under metal/acid free-conditions. The reaction also underscored an intermolecular nitrogen-atom transfer process from TMS-azide leading to final products, where any intermediary azidothiazolidinone was absent. The strategy was extendable to analogous synthesis of Se,N-heterocycles, and furthermore, late-stage drug-modification and follow-up transformations were also performed. Density functional theory calculations and control experiments provided important mechanistic insights and highlighted potential roles of HFIP in the transformation.

Published
2021

7. Zirconium-Catalyzed Hydroalumination of C═O Bonds: Site-Selective De-O-acetylation of Peracetylated Compounds and Mechanistic Insights

Author

Romain M. Q. Renard, Thomas Lecourt, Vincent Gandon, Thibaut Courant, Marine Gavel, and Antoine Joosten

Subjects
Zirconium, 010405 organic chemistry, Hydride, Organic Chemistry, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, chemistry, Catalytic cycle, Acetylation, Site selective, Stoichiometry, Zirconocene dichloride
Abstract

An unprecedented hydroalumination of C ═ O bonds catalyzed by zirconocene dichloride is reported herein and applied to the site-selective deprotection of peracetylated functional substrates. A mixed metal hydride, with 1:1 zirconium/aluminum stoichiometry, is also shown to be the reductive species. A catalytic cycle is finally proposed for this transformation with no precedent in the field of zirconium catalysis.

Published
2021

8. The Piancatelli Reaction

Author

David Lebœuf, Vincent Gandon, Lucile Marin, and Emmanuelle Schulz

Subjects
Chemistry, Organic chemistry
Published
2020

9. Sequential One-Pot Synthesis of 3-Arylbenzofurans from N-Tosylhydrazones and Bromophenol Derivatives

Author

Mouad Alami, Estelle Messe, Hsin-Ping Lin, Vincent Gandon, Camille Hauguel, Diana Lamaa, and Abdallah Hamze

Subjects
010405 organic chemistry, Chemistry, Organic Chemistry, One-pot synthesis, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Radical cyclization, 0104 chemical sciences
Abstract

A divergent and efficient one-pot sequence allowing direct access to 3-arylbenzofuran derivatives has been developed. The process, involving N-tosylhydrazones and bromophenols, proceeds via a palladium-catalyzed Barluenga-Valdes cross-coupling, followed by an aerobic, copper-catalyzed, radical cyclization to form Csp2-Csp2 and O-Csp2 bonds. 3-Arylated benzofurans bearing various substituents were obtained with good to excellent yields (up to 90%). Mechanistic investigation strongly supports a radical process for the cyclization step.

Published
2020

10. On the Superior Activity of In(I) versus In(III) Cations Toward ortho-C-Alkylation of Anilines and Intramolecular Hydroamination of Alkenes

Author

Christophe Bour, Guillaume Thiery, Shengwen Yang, Vincent Gandon, and Zhilong Li

Subjects
inorganic chemicals, 010405 organic chemistry, organic chemicals, digestive, oral, and skin physiology, Organic Chemistry, Cationic polymerization, chemistry.chemical_element, respiratory system, Alkylation, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, 0104 chemical sciences, Catalysis, chemistry, Intramolecular force, heterocyclic compounds, Hydroamination, Indium
Abstract

An efficient ortho-C-alkylation of unprotected anilines with a variety of styrenes and alkenes using a univalent cationic indium(I) catalyst is reported. Mechanistic studies revealed that the react...

Published
2020

11. Exploring the Limits of π‐Acid Catalysis Using Strongly Electrophilic Main Group Metal Complexes: The Case of Zinc and Aluminium

Author

Refka Guermazi, Christophe Bour, Yan Chen, Régis Guillot, Jiaxin Tian, Alexandre Djurovic, Vincent Gandon, Samuel Dagorne, and Marie Vayer

Subjects
Ligand, Organic Chemistry, Cationic polymerization, General Chemistry, Medicinal chemistry, Catalysis, chemistry.chemical_compound, Acid catalysis, Cycloisomerization, chemistry, Main group element, Electrophile, Carbene
Abstract

The catalytic activity of cationic NHC-ZnII and NHC-AlIII (NHC=N-heterocyclic carbene) complexes in reactions that require the electrophilic activation of soft C-C π bonds has been studied. The former proved able to act as a soft π-Lewis acid in a variety of transformations. The benefit of the bulky IPr NHC ligand was demonstrated by comparison with simple ZnX2 salts. The tested NHC-AlIII catalyst is not able to activate C-C π bonds but simple AlX2 + ions were found potent in some cases.

Published
2020

12. Solvent Effect in Gold(I)-Catalyzed Domino Reaction: Access to Furopyrans

Author

Gaëlle Blond, Nayan Ghosh, Patrick Wagner, Vincent Gandon, Laboratoire d'Innovation Thérapeutique (LIT), Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC), Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie moléculaire (LCM), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École polytechnique (X)

Subjects
010405 organic chemistry, Chemistry, Organic Chemistry, Regioselectivity, 010402 general chemistry, 01 natural sciences, Biochemistry, Combinatorial chemistry, 0104 chemical sciences, Catalysis, Solvent, Cascade reaction, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Solvent effects
Abstract

International audience; We report an efficient synthesis of furopyrans through a gold(I)-catalyzed domino reaction. Starting from the same source, and by changing the solvent of the reaction, two classes of furopyrans are accessible. During this one-step process, which takes place in DMF, two bonds and two heterocycles are formed. DFT calculations furnish the mechanistic understanding of this transformation. The sequence includes a 5-endo-dig cyclization, a regioselective 8-endo-dig cyclization, a retro 8p and a 6p electro-cyclization.

Published
2020

13. Aza‐Piancatelli Cyclization as a Platform for the Preparation of Scaffolds of Natural Compounds: Application to the Total Synthesis of Bruceolline D

Author

David Lebœuf, Lucile Marin, Guillaume Force, Emmanuelle Schulz, Vincent Gandon, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Institut de Science et d'ingénierie supramoléculaires (ISIS), Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), and Leboeuf, David

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, [CHIM.THER] Chemical Sciences/Medicinal Chemistry, Organic Chemistry, Total synthesis, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Organic chemistry, Lewis acids and bases, Physical and Theoretical Chemistry, Bruceolline D
Abstract

International audience; The aza‐Piancatelli cyclization provides an expedient synthesis of 4‐aminocyclopentenone building blocks that may be converted into aminocyclopentitols, which are heavily represented motifs among natural products. However, its use as a key step in total synthesis was still unprecedented. Here, we disclose our in‐depth investigations regarding this reaction in order to access highly complex structures representing the core of some natural molecules. The applicability of the cyclization was highlighted by the 3‐step total synthesis of bruceolline D. Thus, we anticipate that this work will lay the ground for further applications in total synthesis

Published
2020

15. Sulfoxide‐Controlled Stereoselective Aza‐Piancatelli Reaction

Author

David Lebœuf, Lucile Marin, Emmanuelle Schulz, Joanna Wencel-Delord, Françoise Colobert, Emilie Kolodziej, Vincent Gandon, Régis Guillot, Soufyan Jerhaoui, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Laboratoire d'innovation moléculaire et applications (LIMA), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Science et d'ingénierie supramoléculaires (ISIS), Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), and Leboeuf, David

Subjects
4aminocyclopentenones, calcium, 010405 organic chemistry, Chemistry, chemistry.chemical_element, Sulfoxide, General Chemistry, aza-Piancatelli cyclization, Calcium, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, chiral sulfoxide, hexafluoroisopropanol, [CHIM] Chemical Sciences, Organic chemistry, [CHIM]Chemical Sciences, Stereoselectivity
Abstract

International audience; The development of a novel stereoselective aza-Piancatelli reaction to access 4aminocyclopentenones is reported. This transformation relies on the use of chiral o-sulfinyl anilines as chiral inductors to afford the targeted products in good to excellent yields. Remarkably, the high value-added cyclopentenones could be obtained in excellent drs (up to > 95:5) depending upon the furan substitution pattern.

Published
2021

16. DFT Analysis into the Calcium(II)-Catalyzed Coupling of Alcohols With Vinylboronic acids: Cooperativity of Two Different Lewis Acids and Counterion Effects

Author

Shengwen Yang, Vincent Gandon, Christophe Bour, David Lebœuf, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Institut de Science et d'ingénierie supramoléculaires (ISIS), Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Leboeuf, David, Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Steric effects, inorganic chemicals, Pericyclic reaction, Coupling Reactions, Cooperativity, 010402 general chemistry, 01 natural sciences, DFT, Catalysis, Computational chemistry, [CHIM] Chemical Sciences, [CHIM]Chemical Sciences, Lewis acids and bases, Superelectrophiles, Group transfer reaction, Lewis Acids, chemistry.chemical_classification, 010405 organic chemistry, Organic Chemistry, Vinylboronic Acids, 0104 chemical sciences, 3. Good health, chemistry, Alcohols, Density functional theory, Calcium, Counterion
Abstract

The mechanism of the calcium-catalyzed coupling of alcohols with vinylboronic acids has been analyzed by means of density functional theory computations. This study reveals that the calcium and boron Lewis acids associate to form a superelectrophile able to promote a pericyclic group transfer reaction with allyl alcohols. With other alcohols, the two Lewis acids act synergistically to activate the OH functionality and trigger a SNi reaction pathway. These two mechanisms are affected by the nature of the counterions, which has been rationalized by electronic and steric factors.

Published
2021

17. Formal [8+3]-Annulation between Azaoxyallyl Cations and Tropones

Author

Régis Guillot, David Leboeuf, Amélie Pérot, Vincent Gandon, Guillaume Force, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire de chimie moléculaire (LCM), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École polytechnique (X)

Subjects
tropone, DFT computations, Reaction conditions, Annulation, -haloamide, 010304 chemical physics, Chemistry, Organic Chemistry, azaoxyallyl cation, 010402 general chemistry, 01 natural sciences, Catalysis, Cycloaddition, 0104 chemical sciences, chemistry.chemical_compound, Computational chemistry, 0103 physical sciences, Tropone, [CHIM.OTHE]Chemical Sciences/Other, cycloaddition
Abstract

International audience; For the first time, azaoxyallyl cations were used as cycloaddition partners with tropone derivatives to access nitrogen-containing [7,6]-fused bicycles in a metal-free process under mild reaction conditions. DFT computations have been used to shed light on the selectivities observed during the course of the reaction.

Published
2019

18. Toward a Greener Barluenga–Valdés Cross-Coupling: Microwave-Promoted C–C Bond Formation with a Pd/PEG/H2O Recyclable Catalytic System

Author

Vincent Gandon, Estelle Messe, Diana Lamaa, Abdallah Hamze, and Mouad Alami

Subjects
010405 organic chemistry, Organic Chemistry, chemistry.chemical_element, Bond formation, 010402 general chemistry, 01 natural sciences, Biochemistry, 0104 chemical sciences, Catalysis, Coupling (electronics), chemistry.chemical_compound, chemistry, XPhos, PEG ratio, Polymer chemistry, Physical and Theoretical Chemistry, Microwave, Palladium
Abstract

A green Barluenga–Valdes cross-coupling reaction for the synthesis of 1,1-diarylethylenes using palladium catalysis has been developed. The new catalytic system based on Pd/Xphos–SO3Na or Pd/MeDave...

Published
2019

19. Calcium(II)- and Triflimide-Catalyzed Intramolecular Hydroacyloxylation of Unactivated Alkenes in Hexafluoroisopropanol

Author

David Lebœuf, Vincent Gandon, Shengwen Yang, Chenxiao Qi, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire de chimie moléculaire (LCM), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École polytechnique (X)

Subjects
chemistry.chemical_classification, 010405 organic chemistry, Chemistry, Bioactive molecules, Organic Chemistry, Salt (chemistry), chemistry.chemical_element, Calcium, 010402 general chemistry, 01 natural sciences, Biochemistry, Combinatorial chemistry, 0104 chemical sciences, Catalysis, Intramolecular force, Surface modification, Reactivity (chemistry), Physical and Theoretical Chemistry, [CHIM.OTHE]Chemical Sciences/Other, ComputingMilieux_MISCELLANEOUS
Abstract

We report an efficient intramolecular hydroacyloxylation of unactivated alkenes, offering a streamlined access to relevant γ-lactones, which features the utilization of either a calcium(II) salt or triflimide as a catalyst in hexafluoroisopropanol. This method could be applied to the synthesis of natural products and the late-stage functionalization of natural and bioactive molecules. Additionally, DFT computations were used to elucidate the twist of reactivity observed between the hydroamidation and hydroacyloxylation of unactivated alkenes regarding the formation of 5- and 6-membered rings.

Published
2019

20. Reaction of Phosphines with 1-Azido-(2-halogenomethyl)benzene Giving Aminophosphonium-Substituted Indazoles

Author

Nicolas Casaretto, Audrey Auffrant, Thibault Tannoux, Vincent Gandon, Sophie Bourcier, Laboratoire de chimie moléculaire (LCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École polytechnique (X), and Institut de Chimie Moléculaire et des Matériaux (MAP/SP2M/ICMMO/UPSaclay-CNRS)

Subjects
Indazole, Bicyclic molecule, 010405 organic chemistry, Organic Chemistry, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, Toluene, 0104 chemical sciences, Adduct, chemistry.chemical_compound, chemistry, Reagent, [CHIM]Chemical Sciences, Benzene, Acetonitrile, Phosphine
Abstract

International audience; The reaction between a 1-azido-(2-halogenomethyl)benzene and a phosphine gives different products depending on the nature of the halogen, the phosphine itself and the solvent employed. While PPh3 (2 equiv.) reacts with the chloro reagent in toluene to give the expected iminophosphorane-phosphonium adduct, trialkylphosphines (PCy3 and PEt3) surprisingly furnish an aminophosphonium substituted by a zwitterionic indazole. The bicyclic product can also form from PPh3 using the bromo reagent in acetonitrile. A mechanism is proposed for this cyclization based on DFT calculations.

Published
2021

21. Concerted vs Nonconcerted Metalation-Deprotonation in Orthogonal Direct C-H Arylation of Heterocycles with Halides: A Computational Study

Author

Vincent Gandon and Christophe Hoarau

Subjects
Deprotonation, 010405 organic chemistry, Chemistry, Metalation, Organic Chemistry, Halide, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, 0104 chemical sciences
Abstract

A computational study on the base-assisted orthogonal C-H arylation of azoles with halides is reported. Although concerted metalation-deprotonation (CMD) is favored under acetate assistance at the C5 site that displays the best balance of nucleophilic and acidic character, the most acidic C2 site may be selectively targeted under carbonate assistance by taking advantage of a carbanionic-type (or non-concerted) metalation-deprotonation mechanism (nCMD). For the latter, several experimental probes including base, ligand, and solvent effects have been collected in favor of an outer-sphere deprotonation process after the formation of a [(L

Published
2021

22. Modular Synthesis of 9,10-Dihydroacridines through an ortho-C Alkenylation/Hydroarylation Sequence between Anilines and Aryl Alkynes in Hexafluoroisopropanol

Author

Vincent Gandon, Yann Sarazin, Christophe Bour, David Lebœuf, Shengdong Wang, Jean-François Carpentier, Guillaume Force, Jonchère, Laurent, Métaux alcalino-terreux pour la fonctionnalisation C–O - - ALCACAT2017 - ANR-17-CE07-0003 - AAPG2017 - VALID, Elaboration d'assemblages supramoléculaires de complexes organométalliques par interactions pi-anioniques et application en catalyse asymétrique - - OREO2016 - ANR-16-CE07-0022 - AAPG2016 - VALID, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Guangzhou University, 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), Institut de Science et d'ingénierie supramoléculaires (ISIS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), ANR French National Research Agency (ANR) [ANR-17-CE07-0003, ANR-16-CE07-0022], CNRS Centre National de la Recherche Scientifique (CNRS) European Commission, Ecole Polytechnique, Universite Paris-Saclay, ANR-17-CE07-0003,ALCACAT,Métaux alcalino-terreux pour la fonctionnalisation C–O(2017), ANR-16-CE07-0022,OREO,Elaboration d'assemblages supramoléculaires de complexes organométalliques par interactions pi-anioniques et application en catalyse asymétrique(2016), 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), Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Matériaux et nanosciences d'Alsace (FMNGE), and Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)

Subjects
Olefin fiber, 010405 organic chemistry, Aryl, Organic Chemistry, Sequence (biology), 010402 general chemistry, 01 natural sciences, Biochemistry, Combinatorial chemistry, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, chemistry, Reaction sequence, Intramolecular force, [CHIM] Chemical Sciences, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry
Abstract

International audience; 9,10-Dihydroacridines are frequently encountered as key scaffolds in OLEDs. However, accessing those compounds from feedstock precursors typically requires multiple steps. Herein, a modular one-pot synthesis of 9,10-dihydroacridine frameworks is achieved through a reaction sequence featuring a selective ortho-C alkenylation of diarylamines with aryl alkynes followed by an intramolecular hydroarylation of the olefin formed as an intermediate. This transformation was accomplished by virtue of the combination of hexafluoroisopropanol and triflimide as a catalyst that triggers the whole process.

Published
2021

23. Tridentate NNN Ligand Associating Amidoquinoline and Iminophosphorane: Synthesis and Coordination to Pd and Ni Centers

Author

Louis Mazaud, Marie Cordier, Audrey Auffrant, Maxime Tricoire, Sophie Bourcier, Vincent Gandon, Laboratoire de chimie moléculaire (LCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École polytechnique (X), Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), and Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
010405 organic chemistry, Ligand, Organic Chemistry, Substituent, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Nickel, chemistry, Physical and Theoretical Chemistry, [CHIM.OTHE]Chemical Sciences/Other
Abstract

International audience; The synthesis of a tridentate NNN ligand incorporating an amidoquinoline and an iminophosphorane (L R H, R =Ph, Cy) was carried out. Coordination to Pd II and Ni II precursors gave as expected square planar complexes of general formula [L R MCl]. The most surprising result came from the reaction of L Ph H with [Ni(COD)2] which gave a Ni II-phenyl complex bearing a tridentate amidoquinoline-aminophosphine ligand. This rearrangement would result from a proton transfer assisted by the Ni 0 when stabilized by a phenyl substituent at the phosphorus, as suggested by DFT calculations and complementary experiments. This nickel-phenyl complex formed the corresponding benzoyl complex under a CO atmosphere.

Published
2020

24. Lewis Acid/Hexafluoroisopropanol: A Promoter System for Selective ortho-C-Alkylation of Anilines with Deactivated Styrene Derivatives and Unactivated Alkenes

Author

Shengdong Wang, Régis Guillot, Christophe Bour, Vincent Gandon, Guillaume Force, David Lebœuf, Yann Sarazin, Jean-François Carpentier, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), 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), Laboratoire de chimie moléculaire (LCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École polytechnique (X), ANR-16-CE07-0022, Agence Nationale de la Recherche, École Polytechnique, Université Paris-Saclay, Centre National de la Recherche Scientifique, ANR-16-CE07-0022,OREO,Elaboration d'assemblages supramoléculaires de complexes organométalliques par interactions pi-anioniques et application en catalyse asymétrique(2016), Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), 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)-Centre National de la Recherche Scientifique (CNRS), École polytechnique (X)-Centre National de la Recherche Scientifique (CNRS), Institut de Science et d'ingénierie supramoléculaires (ISIS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace, Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Université de Strasbourg (UNISTRA)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Université de Strasbourg (UNISTRA), 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), École polytechnique (X)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Université de Rennes 1 (UR1), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace, Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Jonchère, Laurent, and Elaboration d'assemblages supramoléculaires de complexes organométalliques par interactions pi-anioniques et application en catalyse asymétrique - - OREO2016 - ANR-16-CE07-0022 - AAPG2016 - VALID

Subjects
alkenes, 010405 organic chemistry, [CHIM.CATA] Chemical Sciences/Catalysis, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, Alkylation, 010402 general chemistry, anilines, 01 natural sciences, Catalysis, Lewis acid, 0104 chemical sciences, Styrene, chemistry.chemical_compound, ortho-C-alkylation, Aniline, hexafluoroisopropanol, chemistry, [CHIM] Chemical Sciences, Molecule, Surface modification, Organic chemistry, [CHIM]Chemical Sciences, Lewis acids and bases
Abstract

International audience; Aniline derivatives are frequently encountered in molecules of industrial relevance such as dyes or antioxidants, which make the development of synthetic methods for the functionalization of these privileged structures highly sought-after. A general protocol for the hydroarylation of electronically diverse alkenes with anilines would be ideal to provide densely functionalized compounds. However, this transformation has been underexplored compared to more traditional hydroarylation of unactivated alkenes because of the significant challenges associated with the control of the selectivity and its substrate tolerance. Herein, we describe a selective, versatile, and user-friendly ortho-C-alkylation of anilines with alkenes that hinges on the beneficial combination of a Lewis acid (Ca(II)) and hexafluoroisopropanol as a solvent. This protocol allows for the extension of this transformation to highly deactivated styrenes and demonstrates a remarkable improved reactivity regarding aliphatic alkenes, styrene derivatives, and dienes. In addition, DFT computations were performed which, combined with experimental observations, suggest a nearly concerted mechanism that impart the ortho-selectivity.

Published
2020

25. Base-Assisted Intramolecular C–N Coupling Reaction from NH 2 -Bound Cyclopalladated L -Phenylalanine to Indoline-2-carboxylic Acid

Author

Jean-François Brière, Guillaume Journot, Vincent Levacher, Rodolphe Tamion, Aurélien Jacquin-Labarre, Christophe Hoarau, Carlos Afonso, Sébastien Coufourier, Vincent Gandon, Alexandra Le Foll, 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), Oril Industrie, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), and Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Aromatic compounds, Indoles, Carboxylic acid, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, Coupling reaction, Inorganic Chemistry, chemistry.chemical_compound, Organic reactions, Physical and Theoretical Chemistry, chemistry.chemical_classification, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 0104 chemical sciences, chemistry, Organic reaction, Intramolecular force, Mixtures, Indoline, Counterion, Trifluoromethanesulfonate, Palladium
Abstract

International audience; The deprotonative intramolecular-amination reaction of phenylalanine-derived palladacycles has been investigated to highlight a facile carbonate-assisted N–H activation before the C–N bond formation. A major counterion effect led to divergent pathways whereby the SPhos-Pd complexes with iodine, triflate, or trifluoroacetate anions were key intermediates to afford access to (S)-2-indolinecarboxylic acid derivatives.

Published
2020

26. Empirical Estimation of the Molecular Weight of Gold Complexes in Solution by Pulsed-Field Gradient NMR

Author

Jean-Nicolas Dumez, Ghanem Hamdoun, Vincent Gandon, Christophe Bour, 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)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire de chimie moléculaire (LCM), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École polytechnique (X)

Subjects
010405 organic chemistry, Chemistry, Organic Chemistry, Nuclear magnetic resonance spectroscopy, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Catalysis, Inorganic Chemistry, chemistry.chemical_compound, Computational chemistry, Organic synthesis, Physical and Theoretical Chemistry, [CHIM.OTHE]Chemical Sciences/Other, Pulsed field gradient, ComputingMilieux_MISCELLANEOUS
Abstract

Homogenous gold catalysis has emerged as a powerful tool in organic synthesis, but many mechanistic questions in that area remain unanswered. The ability of diffusion-ordered NMR spectroscopy (DOSY...

Published
2018

27. Synthesis of Cyclopenta[b]piperazinones via an Azaoxyallyl Cation

Author

Emmanuelle Schulz, Régis Guillot, Guillaume Force, David Lebœuf, Boubacar Baldé, Lucile Marin, and Vincent Gandon

Subjects
Reaction sequence, 010405 organic chemistry, Chemistry, Organic Chemistry, Physical and Theoretical Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Combinatorial chemistry, 3. Good health, 0104 chemical sciences
Abstract

A new and efficient reaction sequence between 2-furylcarbinols, anilines, and α-haloamides has been developed to afford highly functionalized cyclopenta[ b]piperazinones. This transformation was accomplished through an aza-Piancatelli cyclization/azaoxyallyl cation trapping with a complete control of the diastereoselectivity.

Published
2018

28. Selectivity in the Intermolecular Diels-Alder Reaction of Conjugated Trienes: Experimental and Theoretical Approaches

Author

Fanny Roussi, Vincent Gandon, Camille Remeur, and Sandy Desrat

Subjects
Reaction mechanism, 010405 organic chemistry, Chemistry, Organic Chemistry, Intermolecular force, Conjugated system, 010402 general chemistry, 01 natural sciences, Cycloaddition, 0104 chemical sciences, Computational chemistry, Physical and Theoretical Chemistry, Selectivity, Diels–Alder reaction
Published
2018

29. Dissecting the Gold(I)-Catalyzed Carboaminations of N-Allyl Tetrahydro-β-carbolines to Allenes

Author

Valérian Gobé, Xavier Guinchard, Maxime Dousset, Vincent Gandon, Pascal Retailleau, Institut de Chimie des Substances Naturelles (ICSN), and Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Allylic rearrangement, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Stereochemistry, organic chemicals, Allene, Organic Chemistry, food and beverages, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, Residue (chemistry), chemistry, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS
Abstract

N-Allyl tetrahydro-β-carbolines undergo gold-catalyzed cyclizations that lead to tetracyclic compounds, resulting from both ring closure and the transfer of the allylic group from the nitrogen to the carbon backbone. The final skeleton obtained depends on the nature of both the R2 group of the allene and the R3 group of the allylic residue. Mechanistic studies and DFT calculations allowed the determination of all the mechanistic pathways involved in these processes, stemming from a common intermediate that evolves differently according to the substituents nature.

Published
2018

30. Asymmetric FeII-Catalyzed Thia-Michael Addition Reaction to α,β-Unsaturated Oxazolidin-2-one Derivatives

Author

Thierry Ollevier, Samuel Lauzon, Hoda Keipour, and Vincent Gandon

Subjects
010405 organic chemistry, Chemistry, Organic Chemistry, Enantioselective synthesis, 010402 general chemistry, 01 natural sciences, Biochemistry, Medicinal chemistry, 0104 chemical sciences, Catalysis, Metal, visual_art, visual_art.visual_art_medium, Michael reaction, Carbonyl derivatives, Organic chemistry, Chelation, Physical and Theoretical Chemistry
Abstract

A highly enantioselective FeII-catalyzed thia-Michael addition to α,β-unsaturated carbonyl derivatives was developed. The scope of the reaction was demonstrated with a selection of aromatic, heterocyclic and aliphatic thiols, and various Michael acceptors. The corresponding β-thioethers were obtained in good to excellent yields (up to 98%) and moderate to excellent enantioselectivities (up to 96:4 er). Unusual hepta-coordination of the metal and chelation to α,β-unsaturated oxazolidin-2-one derivatives allowed the construction of a coherent model rationalizing the enantioselective event. DFT calculations support the proposed model for observed stereoselectivities.

Published
2017

31. Triflic Acid as an Efficient Brønsted Acid Promoter for the Umpolung of N-Ac Indoles in Hydroarylation Reactions

Author

Rodolphe Beaud, Didier Gori, Cyrille Kouklovsky, Régis Guillot, Raj Kumar Nandi, Guillaume Vincent, Alejandro Perez-Luna, Vincent Gandon, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Réactivité organométallique et catalyse pour la synthèse (ROCS), Institut Parisien de Chimie Moléculaire (IPCM), and Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Indole test, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, General Chemistry, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, 3. Good health, 0104 chemical sciences, Umpolung, chemistry.chemical_compound, Electrophile, [CHIM]Chemical Sciences, Organic chemistry, Brønsted–Lowry acid–base theory, Friedel–Crafts reaction, Triflic acid, ComputingMilieux_MISCELLANEOUS
Abstract

We report that triflic acid, a strong Bronsted acid, is a very powerful alternative to FeCl3 to mediate the hydroarylation of N-Ac indoles, which delivers regioselectively 3-arylindolines, 3,3-spiroindolines or 2-arylindolines. Mechanistic explorations point towards the existence of a highly electrophilic intermediate by simultaneous activation of the acetyl and of the C2=C3 bond by protons.

Published
2017

32. Revealing the Activity of π-Acid Catalysts using a 7-Alkynyl Cycloheptatriene

Author

Marie Vayer, Christophe Bour, Vincent Gandon, and Régis Guillot

Subjects
010405 organic chemistry, Organic Chemistry, Cycloheptatriene, General Chemistry, 010402 general chemistry, Photochemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Product (mathematics), Polymer chemistry, Lewis acids and bases, Brønsted–Lowry acid–base theory
Abstract

A compound that isomerizes into distinct products depending on the particular Lewis acid or Brønsted acid catalyst used is disclosed. One product can only be obtained with the softest π-acids, such as Au, Pt, Ga, or In complexes. Another is formed only with harder π-acids incorporating Ag or Cu salts. The formation of the third category requires even harder π-acids or protons. This simple benchmark reaction allows for prediction of the category of transformations that can be catalyzed by a new complex. It also informs whether protons have been unintentionally generated in the reaction mixture.

Published
2017

33. Calcium(II)-Catalyzed Alkenylation ofN-Acyliminiums and Related Ions with Vinylboronic Acids

Author

David Lebœuf, Vincent Gandon, and Chenxiao Qi

Subjects
Reaction conditions, 010405 organic chemistry, Chemistry, chemistry.chemical_element, Homogeneous catalysis, General Chemistry, Calcium, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences, Ion, Catalysis, Rapid access, Organic chemistry
Abstract

Efficient C−C bond-forming reactions between N,O-acetals and vinylboronic acids were achieved via a calcium(II)-catalyzed formation of a N-acyliminium intermediate or a related ion. This strategy can give a rapid access to a wide variety of alkenyl-functionalized nitrogen-containing compounds in good to excellent yields under simple reaction conditions.

Published
2017

34. Carbon–Carbon and Carbon–Heteroatom Bond-Forming Transformations Catalyzed by Calcium(II) Triflimide

Author

David Lebœuf and Vincent Gandon

Subjects
chemistry.chemical_classification, 010405 organic chemistry, Organic Chemistry, Heteroatom, Reinforced carbon–carbon, Salt (chemistry), Substrate (chemistry), chemistry.chemical_element, Calcium, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, chemistry, Nucleophile, Organic chemistry, Carbon
Abstract

The aim of this short review is to highlight the interest of using Ca(NTf2)2 as catalyst in C–C and C–X bond-forming reactions. The ability of this complex to activate alcohols, alkenes, ketones, and cyclopropanes towards nucleophilic additions and other chemical processes is shown though a set of selected examples, which illustrate the substrate scope and the synthetic applications offered by this ‘green’ calcium salt. 1 Introduction 2 Synthetic Applications 3 Conclusion

Published
2017

35. Acid-catalysed intramolecular addition of β-ketoesters to 1,3-dienes

Author

Weizhen Fang, Christophe Bour, Vincent Gandon, Régis Guillot, Marie Vayer, and Sophie Bezzenine-Lafollée

Subjects
Mesylates, Molecular Structure, 010405 organic chemistry, Chemistry, Organic Chemistry, Esters, Ketones, Bond formation, 010402 general chemistry, 01 natural sciences, Biochemistry, Medicinal chemistry, Catalysis, 0104 chemical sciences, Alkadienes, Cyclization, Intramolecular force, Rare case, Molecule, Physical and Theoretical Chemistry
Abstract

1,3-Dienyl β-keto esters are cyclised into bicyclolactones using the Bi(OTf)3/TfOH catalytic system. This reaction represents a rare case of simultaneous C–C and C–O bond formation at positions 1 and 3 of a 1,3-diene. Application to the synthesis of ramulosin is presented.

Published
2017

36. Asymmetric Cu I -Catalyzed Insertion Reaction of 1-Aryl-2,2,2-trifluoro-1-diazoethanes into Si–H Bonds

Author

Vincent Gandon, Virginie Carreras, Claire Besnard, Thierry Ollevier, Département de Chimie, Université Laval, Université Laval [Québec] (ULaval), Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire de chimie moléculaire (LCM), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École polytechnique (X)

Subjects
010405 organic chemistry, Aryl, Organic Chemistry, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Biochemistry, Copper, 0104 chemical sciences, Catalysis, Solvent, chemistry.chemical_compound, chemistry, Insertion reaction, Polymer chemistry, Physical and Theoretical Chemistry, Dimethyl carbonate, [CHIM.OTHE]Chemical Sciences/Other, ComputingMilieux_MISCELLANEOUS
Abstract

An asymmetric copper(I)-catalyzed Si–H insertion reaction of 1-aryl-2,2,2-trifluoro-1-diazoethanes in dimethyl carbonate as a green solvent alternative was developed. A C2-symmetric copper(I) diimi...

Published
2019

37. Enantioselective Gold-Catalyzed Pictet-Spengler Reaction

Author

Shengwen Yang, Vincent Gandon, Pascal Retailleau, Nicolas Glinsky-Olivier, Xavier Guinchard, 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)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire de chimie moléculaire (LCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École polytechnique (X), and Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)

Subjects
Indole test, Pictet–Spengler reaction, 010405 organic chemistry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Enantioselective synthesis, Cationic polymerization, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 01 natural sciences, Biochemistry, Combinatorial chemistry, 0104 chemical sciences, Catalysis, Tryptamines, chemistry.chemical_compound, Yield (chemistry), Functional group, Physical and Theoretical Chemistry, [CHIM.OTHE]Chemical Sciences/Other, ComputingMilieux_MISCELLANEOUS
Abstract

International audience; Cationic chiral Au(I) complexes catalyze asymmetric Pictet−Spengler reactions between tryptamines and arylaldehydes. The resulting tetrahydro-β-carbolines are obtained with wide functional group tolerance in high yield and with high enantioselectivities (up to 95%). Aldehydes bearing polar or protic functions are well tolerated. The reaction features a hitherto unknown C2-auration of the indole as the key step, supported by density functional theory calculations.

Published
2019

38. Enantioselective Synthesis of Complex Fused Heterocycles through Chiral Phosphoric Acid Catalyzed Intramolecular Inverse-Electron-Demand Aza-Diels-Alder Reactions

Author

Lucie Jarrige, Géraldine Masson, Vincent Gandon, Institut de Chimie des Substances Naturelles (ICSN), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie moléculaire (LCM), École polytechnique (X)-Centre National de la Recherche Scientifique (CNRS), and Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Organic Chemistry, Enantioselective synthesis, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Catalysis, Cycloaddition, 0104 chemical sciences, Bifunctional catalyst, chemistry.chemical_compound, Intramolecular force, Povarov reaction, [CHIM.OTHE]Chemical Sciences/Other, Enantiomeric excess, Mannich reaction, Phosphoric acid, ComputingMilieux_MISCELLANEOUS
Abstract

A stable asymmetric intramolecular Povarov reaction has been established to provide an efficient method to access structurally diverse trans,trans-trisubstituted tetrahydrochromeno[4,3-b]quinolines in high stereoselectivities of up to >99:1 diastereomeric ratio and 99 % enantiomeric excess, without any purification step. Additionally, to facilitate large-scale application of this method, a low catalyst loading protocol was employed, 0.2 mol % chiral phosphoric acid, which provided the cycloadducts without any loss in yield and enantioselectivity. Theoretical studies revealed that the reaction occurred through a sequential Mannich reaction and an intramolecular Friedel-Crafts reaction, wherein the phosphoric acid acted as a bifunctional catalyst to activate the para-phenolic dienophile and N-2-hydroxy-2-azadiene simultaneously.

Published
2019

39. Synthesis of Medium-Sized Carbocycles by Gallium-Catalyzed Tandem Carbonyl–Olefin Metathesis/Transfer Hydrogenation

Author

Régis Guillot, Marie Vayer, Alexandre Djurovic, Jean-Pierre Baltaze, Vincent Gandon, Zhilong Li, Christophe Bour, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire de chimie moléculaire (LCM), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École polytechnique (X)

Subjects
Cyclopentanes, Tandem, 010405 organic chemistry, Organic Chemistry, Cationic polymerization, chemistry.chemical_element, 010402 general chemistry, Transfer hydrogenation, Metathesis, 01 natural sciences, Biochemistry, Combinatorial chemistry, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, chemistry, Functional group, Physical and Theoretical Chemistry, Gallium, [CHIM.OTHE]Chemical Sciences/Other, ComputingMilieux_MISCELLANEOUS
Abstract

We report a catalytic tandem process involving a ring-closing carbonyl-olefin metathesis and a transfer hydrogenation. 1,4-Cyclohexadiene has been used as H2 surrogate to reduce the cyclic alkenes formed after the metathesis step. The same NHC-stabilized cationic gallium(III) complex, [IPr˙GaCl2][SbF6], performs the two steps with functional group tolerance. This reaction is stereoselective, leading either to 1,2-cisdisubstituted cyclopentanes or to a variety of cyclohexanes. DFT computations support an unexpected mechanism involving the activation of 1,4-cyclohexadiene by superelectrophilic gallium(III) dimers.

Published
2019

40. Ring Expansion and 1,2-Migration Cascade of Benzisoxazoles with Ynamides: Experimental and Theoretical Studies

Author

B. Prabagar, Akhila K. Sahoo, Rajeshwer Vanjari, Vincent Gandon, Shubham Dutta, School of Chemistry, University of Hyderabad, University of Hyderabad, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire de chimie moléculaire (LCM), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École polytechnique (X)

Subjects
Annulation, 010405 organic chemistry, Stereochemistry, Organic Chemistry, Benzisoxazole, General Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, 3. Good health, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, chemistry, Cascade, Stereoselectivity, [CHIM.OTHE]Chemical Sciences/Other, Carbene, ComputingMilieux_MISCELLANEOUS
Abstract

Demonstrated herein is an AuI -catalyzed annulation of sulfonyl-protected ynamides with substituted 1,2-benzisoxazoles for the synthesis of E-benzo[e][1,3]oxazine derivatives. The transformation involves the addition of benzisoxazole to the gold-activated ynamide, ring expansion of the benzisoxazole fragment to provide an α-imino vinylic gold intermediate, and 1,2-migration of the sulfonamide motif to the masked carbene center to deliver the respective ring-expanded benzo[e][1,3]oxazine of predominant E configuration. A trapping experiment justifies the participation of the α-imino masked gold carbene. DFT computations also support the hypothesized mechanism and rationalize the product stereoselectivity.

Published
2019

41. Gold(I)-Catalyzed Synthesis of Furopyrans: Insight into Hetero-Diels–Alder Reactions

Author

Nayan Ghosh, Vincent Gandon, Gaëlle Blond, Patrick Wagner, Romain Pertschi, Laboratoire d'Innovation Thérapeutique (LIT), Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC), Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie moléculaire (LCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École polytechnique (X), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS), École polytechnique (X)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie des Substances Naturelles (ICSN), and Centre National de la Recherche Scientifique (CNRS)

Subjects
Diene, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Combinatorial chemistry, 0104 chemical sciences, Stereocenter, Catalysis, chemistry.chemical_compound, chemistry, Cascade reaction, Diels alder, Molecule, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, [CHIM.OTHE]Chemical Sciences/Other, ComputingMilieux_MISCELLANEOUS
Abstract

International audience; We report herein the synthesis of complex molecules containing furopyran cores through a gold(I)-catalyzed hetero Diels-Alder cascade reaction. During this process, the diene and the dienophile are produced concomitantly by the action of a single catalyst from a single starting material. Moreover, six bonds, four heterocycles and four controlled stereogenic centers are formed in a one-step operation. DFT calculations provide the mechanistic basis of this unprecedented reaction. The last 30 years have witnessed an upsurge in the development of methodologies enabling the synthesis of intricate molecular scaffolds from simple precursors. In addition to these new synthetic strategies, the quest for molecular complexity has often resulted in important fundamental insight into selectivity principles. 1 A particularly promising strategy to rapidly construct complex molecules is to trigger domino reactions that convert simple starting materials into highly sophisticated targets by creating several bonds in a one-pot operation. 2 Achieving complexity with brevity is indeed a key to ideal synthesis. The use of transition metal-catalyzed transformations as part of a domino process considerably decreases the energy cost of the overall transformation and favors highly selective reactions due to the pre-organization of the reactive intermediates around the metallic center. In particular, homogeneous gold(I)-catalyzed reactions have attracted much attention because of the great diversity of original and complex molecules that can be obtained from adequately designed substrates, under mild reaction conditions. 3 Recently, few methodologies have been developed using gold(I)-catalysis in domino processes, including hetero Diels-Alder reactions. The hetero Diels-Alder reaction (HDA) is among the most efficient methods for the synthesis of functionalized heterocycles with control of regio-, diastereo-and enantioselectivity. 4 Most of the gold(I)-triggered HDA reported so far rely on the in situ generation of the diene and/or of the dienophile, starting with two different reagents. 5 However, HDA between diene and dienophile obtained from single starting substrate using gold-catalyst remains elusive. We report herein the synthesis of complex polycyclic molecules 4 containing furopyran cores of interest 6 through a gold(I)-catalyzed domino reaction involving HDA (Scheme 1). During this process, both of the dienophile 2 and the diene 3 are produced concomitantly by the action of a single catalyst from a single starting material 1. To our knowledge, this concept has never been exploited. Moreover, during this transformation , six bonds, four heterocycles and four controlled stere-ogenic centers are formed in a one-step operation with 100% atom economy. DFT calculations provide the mechanistic insight of this unprecedented reaction. Scheme 1. Gold(I)-catalyzed hetero Diels-Alder cascade reaction for the synthesis of furopyrans derivatives 4.

Published
2019

42. Gold‐Catalyzed Regioselective Tetradehydro‐Diels‐Alder Reaction of Yne‐Ynamides: Access to 2,3‐Dihydrobenzo[ f ]indoles

Author

Akhila K. Sahoo, Vincent Gandon, Shubham Dutta, B. Prabagar, School of Chemistry, University of Hyderabad, University of Hyderabad, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire de chimie moléculaire (LCM), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École polytechnique (X)

Subjects
Indole test, 010405 organic chemistry, Aryl, Organic Chemistry, Regioselectivity, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, Cycloaddition, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, chemistry, Intramolecular force, Density functional theory, [CHIM.OTHE]Chemical Sciences/Other, ComputingMilieux_MISCELLANEOUS, Diels–Alder reaction
Abstract

Presented herein is a gold(I) catalyzed intramolecular tetradehydro-Diels-Alder (TDDA) reaction of alkyne-tethered-ynamides for the construction of structurally complex 2,3-dihydrobenzo[f]indole derivatives. The mechanism of the regioselective benzannulation reaction was rationalized by means of density functional theory (DFT) calculations. Substrates having an aryl group at the ynamide terminus are exclusively participating in this TDDA reaction under gold catalysis.

Published
2019

43. Stereoselective Access to ( E )-1,3-Enynes through Pd/Cu-Catalyzed Alkyne Hydrocarbation of Allenes

Author

Vincent Gandon, Remy Kouoi, Anne Regazzetti, Guillaume Masson, Grégory Genta-Jouve, Emmanuel Roulland, Louis Jeanne-Julien, Cibles Thérapeutiques et conception de médicaments (CiTCoM - UMR 8038), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Descartes - Paris 5 (UPD5), Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire de chimie moléculaire (LCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École polytechnique (X), Université Paris Descartes - Paris 5 (UPD5)-Centre National de la Recherche Scientifique (CNRS), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS), and École polytechnique (X)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, 010405 organic chemistry, Organic Chemistry, Substrate (chemistry), Alkyne, 010402 general chemistry, 01 natural sciences, Biochemistry, Oxidative addition, Combinatorial chemistry, 0104 chemical sciences, Catalysis, chemistry, Catalytic cycle, Atom economy, Stereoselectivity, Physical and Theoretical Chemistry, [CHIM.OTHE]Chemical Sciences/Other, ComputingMilieux_MISCELLANEOUS
Abstract

PdII and CuI cooperate in catalyzing the alkynes hydrocarbation of allenes (AHA) giving (E)-1,3-enynes with high yields, atom economy, and high regio-/stereoselectivities. We devised new efficient conditions and expanded the substrate scope. Experimental and computational studies support a nonorthodox PdII/PdIV catalytic cycle involving an oxidative addition triggered by a stereodeterminant H+ transfer. This reaction is leveraged in a new strategy of stereoselective synthesis of 1,3-dienes.

Published
2019

44. Gold-Catalyzed syn-1,2-Difunctionalization of Ynamides via Nitrile Activation

Author

Shubham Dutta, Rajeshwer Vanjari, Manash Protim Gogoi, Vincent Gandon, and Akhila K. Sahoo

Subjects
Nitrile, 010405 organic chemistry, Chemistry, Organic Chemistry, Regioselectivity, 010402 general chemistry, 01 natural sciences, Biochemistry, Combinatorial chemistry, 0104 chemical sciences, Catalysis, Coupling (electronics), chemistry.chemical_compound, Density functional theory, Physical and Theoretical Chemistry
Abstract

Developed is an unprecedented Au(I)-catalyzed syn-1,2-difunctionalization of ynamides with 2-aminobenzonitriles via nitrile activation. The coupling between ynamides and 2-aminobenzonitriles is explicitly regioselective, providing a straightforward access to 2,4-diamino-substituted quinolines. Density functional theory (DFT) study provides insightful information and rationalizes the reaction pathway. It shows how the synergy between ynamide π-activation and nitrile σ-coordination by the Au(I) catalyst makes the cyclization viable.

Published
2018

45. Calcium-Catalyzed Synthesis of Polysubstituted 2-Alkenylfurans from β-Keto Esters Tethered to Propargyl Alcohols

Author

David Leboeuf, Sara P. Morcillo, Vincent Gandon, and Christophe Bour

Subjects
010405 organic chemistry, Chemistry, Organic Chemistry, chemistry.chemical_element, Alcohol, General Chemistry, Calcium, Carbocation, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, Furan, Propargyl, Organic chemistry, Tertiary alcohols
Abstract

An efficient synthesis of polysubstituted 2-alkenylfurans using Ca(NTf2 )2 /KPF6 as a catalytic mixture is described. It is based on the cycloelimination of readily available propargyl alcohols tethered to β-keto esters under dry conditions to avoid competitive Meyer-Schuster rearrangement. The furan can be further functionalized in situ by a calcium-catalyzed Friedel-Crafts-type reaction with secondary and tertiary alcohols. The title reaction allows for the high-yielding preparation of di-, tri-, and tetrasubstituted 2-alkenylfurans, which are important subunits of bioactive compounds.

Published
2016

46. Rhodium-Catalyzed Alkene Difunctionalization with Nitrenes

Author

Philippe Dauban, Jennifer Ciesielski, Pascal Retailleau, Geoffroy Dequirez, and Vincent Gandon

Subjects
chemistry.chemical_classification, Intramolecular reaction, 010405 organic chemistry, Alkene, Nitrene, Organic Chemistry, chemistry.chemical_element, General Chemistry, Aziridine, 010402 general chemistry, Photochemistry, 01 natural sciences, Medicinal chemistry, Catalysis, 0104 chemical sciences, Rhodium, chemistry.chemical_compound, Nucleophile, chemistry, Electrophile, Amination
Abstract

The Rh(II) -catalyzed oxyamination and diamination of alkenes generate 1,2-amino alcohols and 1,2-diamines, respectively, in good to excellent yields and with complete regiocontrol. In the case of diamination, the intramolecular reaction provides an efficient method for the preparation of pyrrolidines, and the intermolecular reaction produces vicinal amines with orthogonal protecting groups. These alkene difunctionalizations proceed by aziridination followed by nucleophilic ring opening induced by an Rh-bound nitrene generated in situ, details of which were uncovered by both experimental and theoretical studies. In particular, DFT calculations show that the nitrogen atom of the putative [Rh]2 =NR metallanitrene intermediate is electrophilic and support an aziridine activation pathway by N⋅⋅⋅N=[Rh]2 bond formation, in addition to the N⋅⋅⋅[Rh]2 =NR coordination mode.

Published
2016

47. Chiral Phosphate in Rhodium-Catalyzed Asymmetric [2+2+2] Cycloaddition: Ligand, Counterion, or Both?

Author

Louis Fensterbank, Corinne Aubert, Elsa Caytan, Marion Barbazanges, Denis Lesage, Cyril Ollivier, Vincent Gandon, 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), 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), Institut de Chimie des Substances Naturelles (ICSN), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), 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), CNRS, UPMC, ANR-09-BLAN-108 SACCAOR, Agence Nationale de la Recherche, IUF, 2006-013, CRIHAN, ANR-09-BLAN-0108,SACCAOR,Stratégie de l'Anion Chiral en Catalyse Asymétrique Organométallique(2009), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-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
Stereochemistry, chirality, chemistry.chemical_element, Homogeneous catalysis, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, Catalysis, Rhodium, [CHIM]Chemical Sciences, ligand effects, cycloaddition, chemistry.chemical_classification, 010405 organic chemistry, Chemistry, Ligand, Organic Chemistry, General Chemistry, homogeneous catalysis, Cycloaddition, 3. Good health, 0104 chemical sciences, rhodium, Stereoselectivity, Counterion, Chirality (chemistry)
Abstract

International audience; Investigations based on NMR spectroscopy, mass spectrometry, and DFT calculations shed light on the metallic species generated in the rhodium-catalyzed asymmetric [2+2+2] cycloaddition reaction between diynes and isocyanates with the chiral phosphate TRIP. The catalytic mixture comprising [{Rh(cod)Cl}2 ], 1,4-diphenylphosphinobutane (dppb), and Ag(S)-TRIP actually gives rise to two species, both having an effect on the stereoselectivity. One is a rhodium(I) complex in which TRIP is a weakly coordinating counterion, whereas the other is a bimetallic Rh/Ag complex in which TRIP is a strongly coordinating X-type ligand.

Published
2016

48. Site-Selective Calcium-Catalyzed/Organocatalyzed Condensation of Propargyl Alcohols Tethered to β-Keto Esters

Author

Vincent Coeffard, Marc Presset, Christophe Bour, Sébastien Floquet, Vincent Gandon, Christine Greck, and Sara P. Morcillo

Subjects
Trifluoromethyl, 010405 organic chemistry, Organic Chemistry, Regioselectivity, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Aldol reaction, Nucleophile, Organocatalysis, Propargyl, Electrophile, Organic chemistry, Aldol condensation, Physical and Theoretical Chemistry
Abstract

The intramolecular condensation of β-keto esters to give propargyl alcohols is described. The substrates have two electrophilic sites and two nucleophilic sites. The site selectivity can be fully controlled. In the presence of a calcium-based catalyst and under anhydrous conditions, O-addition products are isolated. On the other hand, traces of water or iPrOH as additive encourage calcium-catalyzed Meyer–Schuster rearrangements. The resulting enones may be further transformed into endo-Michael addition products. The regioselectivity of the attack of the enolate can be changed by using 1-[3,5-bis(trifluoromethyl)phenyl]-3-[2-(dimethylamino)cyclohexyl]thiourea (TUC) as organocatalyst, which promotes the formation of aldol-condensation products of high synthetic interest. DFT calculations rationalize the preference for the aldol condensation when TUC is used instead of the endo-Michael addition.

Published
2016

49. Iodine-Catalyzed Iso-Nazarov Cyclization of Conjugated Dienals for the Synthesis of 2-Cyclopentenones

Author

Jorgelina L. Pergomet, Lucía A. Marsili, Martín J. Riveira, and Vincent Gandon

Subjects
inorganic chemicals, 010405 organic chemistry, Organic Chemistry, Ciencias Químicas, chemistry.chemical_element, Conjugated system, 010402 general chemistry, Iodine, 01 natural sciences, Biochemistry, DIENALS, 0104 chemical sciences, Catalysis, IODINE CATALYSIS, Cycloisomerization, Química Orgánica, chemistry, Iodine catalysis, CYCLOPENTENONES, Organic chemistry, Physical and Theoretical Chemistry, Efficient catalyst, HALOGEN CATALYSIS, CIENCIAS NATURALES Y EXACTAS
Abstract

Molecular iodine was identified as an efficient catalyst for the cycloisomerization of conjugated dienals to substituted 2-cyclopentenones. DFT calculations suggested an unexpected concerted character for this cyclization. Fil: Marsili, Lucía A.. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas; Argentina Fil: Pergomet, Jorgelina Leonor. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: Gandon, Vincent. Universite de Paris XI. Institut de Chimie Moléculaire et des Matériaux d'Orsay; Francia Fil: Riveira, Martín Jorge. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina

Published
2018

50. Gallium-Catalyzed Scriabine Reaction

Author

Manish Pareek, Christophe Bour, Vincent Gandon, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire de chimie moléculaire (LCM), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École polytechnique (X)

Subjects
010405 organic chemistry, Organic Chemistry, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Biochemistry, Combinatorial chemistry, Enol, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, chemistry, Physical and Theoretical Chemistry, Gallium, [CHIM.OTHE]Chemical Sciences/Other, ComputingMilieux_MISCELLANEOUS
Abstract

γ-Aryl enol acetates are easily obtained from diacetoxy alkenes and electron-rich arenes at room temperature using GaCl3 as catalyst. The products can then be converted into β-aryl aldehydes. This method represents the first broadly applicable catalytic version of the Scriabine reaction. DFT computations shed light on the mechanism of this transformation.

Published
2018

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