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149 results on '"Thierry Constantieux"'

51. A temporary-bridge strategy for enantioselective organocatalyzed synthesis of aza-seven-membered rings

Author

Thierry Constantieux, Damien Bonne, Sébastien Goudedranche, Jean Rodriguez, David Pierrot, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC), ANR-11-BS07-0014,OEREKA,Réactions Enantiosélectives Organocatalysées à partir de Cétoamides(2011), and Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Annulation, azepanes, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Stereochemistry, Chemistry, domino reactions, Metals and Alloys, Enantioselective synthesis, General Chemistry, Optically active, Catalysis, Domino, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry.chemical_compound, Azepane, Electrophile, Materials Chemistry, Ceramics and Composites, enantioselective organocatalysis
Abstract

International audience; We report the first enantioselective organocatalyzed domino synthesis of azepane moieties. This temporary-bridge strategy is based on a conceptually original annulation of ambident electrophilic and 1,4-bis-nucleophilic a-ketoamides with 1,3-bis-electrophilic enals. The obtained oxygen-bridged azepanes can be selectively transformed into optically active azepanone, azepanol or azepanedione derivatives of high synthetic value.

Published
2014
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52. ChemInform Abstract: Organocatalytic Enantioselective Multicomponent Synthesis of Pyrrolopiperazines

Author

Xavier Bugaut, Haiying Du, Thierry Constantieux, and Jean Rodriguez

Subjects
chemistry.chemical_classification, chemistry, Enantioselective synthesis, General Medicine, Combinatorial chemistry, Tricyclic
Abstract

Original and biologically relevant fused tricyclic piperazines are synthesized via this new organocatalytic multicomponent reaction.

Published
2014
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53. Organocatalytic enantio- and diastereoselective conjugate addition to nitroolefins: when beta-ketoamides surpass beta-ketoesters

Author

Thierry Constantieux, Haiying Du, Xavier Bugaut, Jean Rodriguez, STeRéO, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Enantioselective synthesis, General Chemistry, 010402 general chemistry, diastereoselectivity, 01 natural sciences, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, chemistry, ketoamides, Amide, Michael addition, nitroolefins, enantioselectivity, Michael reaction, Organic chemistry, Reactivity (chemistry), Methylene, Selectivity, Bifunctional, Conjugate
Abstract

International audience; Our findings on the bifunctional squaramide-catalyzed enantioselective conjugate addition of β-ketoamides to nitroolefins are disclosed. It appears that simple acyclic methylene β-ketoamides, unlike the extensively studied β-ketoesters, afford the products in excellent diastereoselectivities, and maintain high yields and enantioselectivities. Moreover, competition and kinetic studies were conducted to rationalize the observed reactivity and selectivity. The high level of diastereocontrol, along with the amenability of the amide group to postfunctionalization, dramatically increase the synthetic usefulness of the transformation.

Published
2014
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54. ChemInform Abstract: α,β-Unsaturated Acyl Cyanides as New Bis-Electrophiles for Enantioselective Organocatalyzed Formal [3 + 3] Spiroannulation

Author

Jean Rodriguez, Damien Bonne, Sébastien Goudedranche, Xavier Bugaut, and Thierry Constantieux

Subjects
Acylation, Chemistry, Stereochemistry, Organocatalysis, Electrophile, Enantioselective synthesis, Reactivity (chemistry), General Medicine, Optically active, Ring (chemistry), Domino
Abstract

α,β-Unsaturated acyl cyanides are key bis-electrophile substrates for successful domino enantioselective organocatalyzed Michael-intramolecular acylation domino sequences. This new reactivity has been applied to the synthesis of enantioenriched azaspiro[4,5]decanone ring systems by a formal [3+3]spiroannulation, constituting a rare example of synthesis of glutarimides in an optically active form.

Published
2014
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55. Enantioselective cascade formal reductive insertion of allylic alcohols into the C(O)Cbond of 1,3-diketones: ready access to synthetically valuable 3-alkylpentanol units

Author

Thierry Constantieux, Adrien Quintard, Mylène Roudier, Jean Rodriguez, STeRéO, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)

Subjects
Allylic rearrangement, 010405 organic chemistry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, organic chemicals, Organic Chemistry, Enantioselective synthesis, asymmetric catalysis, 010402 general chemistry, 01 natural sciences, Biochemistry, Redox, 0104 chemical sciences, iron, Cascade reaction, Cascade, Yield (chemistry), dual catalysis, hydrogen transfer, Molecule, Organic chemistry, organocatalysis, Physical and Theoretical Chemistry
Abstract

International audience; An unprecedented cascade reaction combining dual iron−amine-catalyzed enantioselective functionalization of allylic alcohols and chemoselective acyl transfer is presented. It allows, from diketones and allylic alcohols, preparation of efficiently functionalized γ-chiral alcohols in up to 96% yield and 96:4 er. The interest of this redox-, atom-, and step-economomical approach was further demonstrated in the short synthesis of several key fragments of biologically active natural products or odorant molecules.

Published
2014
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56. ChemInform Abstract: Enantioselective Organocatalytic Multicomponent Synthesis of 2,6-Diazabicyclo[2.2.2]octanones

Author

Xavier Bugaut, Yves Génisson, Jean Rodriguez, Jean-Christophe Plaquevent, Maria del Mar Sanchez Duque, Thierry Constantieux, and Olivier Baslé

Subjects
Octanone, chemistry.chemical_compound, Chemistry, Organocatalysis, Acrolein, Enantioselective synthesis, Organic chemistry, Amine gas treating, General Medicine, Bifunctional, Catalysis, Stereocenter
Abstract

The title reaction of β-ketoamides, acrolein, and aminophenols, catalyzed by a bifunctional thiourea-tertiary amine organocatalyst, enables the preparation of an enantioenriched diazabicyclo[2.2.2]octanone (2,6-DABCO) scaffold. The chemoselective reaction sequence installs five new bonds and three stereocenters, two of which are contiguous tetrasubstituted centers, with excellent yields and high levels of stereocontrol. M.S.=molecular sieves

Published
2014
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57. ChemInform Abstract: An Iron/Amine-Catalyzed Cascade Process for the Enantioselective Functionalization of Allylic Alcohols

Author

Jean Rodriguez, Adrien Quintard, and Thierry Constantieux

Subjects
Allylic rearrangement, Chemistry, Cascade, Scientific method, Enantioselective synthesis, Surface modification, Amine gas treating, General Medicine, Combinatorial chemistry, Catalysis
Abstract

A novel bicatalytic system consisting of an in situ generated Fe-complex, obtained by CO-decoordination with Me3NO, and L-diphenylsilylprolinol allows the transformation of allylic alcohols into β-chiral alcohols with high enantioselectivities (up to 90% e.e.).

Published
2014
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58. Design of a new class of chiral quinoline–phosphine ligands. Synthesis and application in asymmetric catalysis

Author

Guillaume Delapierre, Jean Michel Brunel, Thierry Constantieux, and Gérard Buono

Subjects
Substitution reaction, Allylic rearrangement, Organic Chemistry, Quinoline, Enantioselective synthesis, Diethylzinc, Catalysis, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Organocatalysis, Organic chemistry, Physical and Theoretical Chemistry, Phosphine
Abstract

The design and synthesis of a new class of chiral quinoline–phosphine ligands has been achieved. Their efficiency as asymmetric ligands in enantioselective palladium-catalyzed allylic substitution reactions and in the asymmetric copper-catalyzed addition of diethylzinc to enones was also investigated.

Published
2001
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59. Enantioselective Conjugate Addition of Diethylzinc to Enones with Chiral Copper-QUIPHOS Catalyst Influence of the Addition of Water on the Enantioselectivity

Author

Jean Michel Brunel, Guillaume Delapierre, Gérard Buono, and Thierry Constantieux

Subjects
chemistry.chemical_compound, Ligand, Chemistry, Organic Chemistry, Enantioselective synthesis, chemistry.chemical_element, Physical and Theoretical Chemistry, Diethylzinc, Enantiomeric excess, Combinatorial chemistry, Copper, Conjugate, Catalysis
Abstract

The use of a new chiral copper catalyst involving QUIPHOS as ligand in the 1,4-addition of Et2Zn to enones is reported. The dramatic beneficial effect of addition of water or Zn(OH)2 to this system has been investigated, and led to an improvement of the enantiomeric excess from 7 to 61% ee.

Published
2000
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60. Highly Efficient Access to Original Polycyclic Pyrrolopiperazine Scaffolds by a Three-Component Reaction with 1,3-Dicarbonyls

Author

Frederic Lieby‐Muller, Thierry Constantieux, Jean Rodriguez, STeRéO, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
atom economy, multicomponent reaction, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Organic Chemistry, 3-dicarbonyls, General Medicine, 010402 general chemistry, Molecular sieve, Heterogeneous catalysis, 01 natural sciences, Combinatorial chemistry, Environmentally friendly, 0104 chemical sciences, heterogeneous catalysis, Cascade reaction, molecular sieves, Atom economy, Component (UML), Organic chemistry, pyrrolopiperazine
Abstract

International audience; Molecular sieves have been found to promote a new fast, environmentally friendly and experimentally simple mul- ticomponent domino reaction from 1,3-dicarbonyls for the synthe- sis of pyrrolopiperazine and azasteroid-like scaffolds, of potential synthetic and biological interests.

Published
2007
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61. New chiral o-hydroxyphenyl diazaphospholidine oxide. Catalytic application in asymmetric addition of diethylzinc to aromatic aldehydes

Author

Gérard Buono, Olivier Legrand, Jean Michel Brunel, and Thierry Constantieux

Subjects
organic chemicals, Organic Chemistry, Oxide, Diethylzinc, Biochemistry, Chiral diamine, Catalysis, Solvent, chemistry.chemical_compound, chemistry, Drug Discovery, polycyclic compounds, Organic chemistry, heterocyclic compounds, Enantiomer
Abstract

Synthesis of diastereomerically pure o-hydroxyphenyl diazaphospholidine oxide 2 was achieved from a chiral diamine derived from (S)-proline. This new compound has been tested as catalyst in the asymmetric addition of diethylzinc to aromatic aldehydes. Corresponding sec-alcohols were obtained in high yields (up to 90%) with enantiomeric excesses varying from 15 to >99%. The influence of the solvent and also the important relation existing between the nature of the aldehydes and the enantioselectivity have been investigated.

Published
1998
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62. Organocatalytic Enantioselective Multicomponent Synthesis of Pyrrolopiperazines

Author

Haiying Du, Xavier Bugaut, Jean Rodriguez, Thierry Constantieux, STeRéO, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC), and Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)

Subjects
010405 organic chemistry, Chemistry, multicomponent reactions, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Enantioselective synthesis, Iminium, General Chemistry, Enantioselectivity, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, Reaction sequence, pyrrolopiperazines, Organocatalysis, Michael addition, Michael reaction, organocatalysis, Pyrrole
Abstract

International audience; The first organocatalytic multicomponent synthesis of enantioenriched pyrrolopiperazines is reported. These biologically relevant fused tricyclic products were obtained under catalytic iminium activation through a reaction sequence involving an enantioselective Michael addition followed by an iminium ion trapping via Pictet-Spengler cyclization (MAPS sequence). Substantial possibilities for variation on the three reaction partners [β-keto ester, enal and N-(2-aminoethyl)pyrrole] along with excellent enantioselectivities are the highlights of the present transformation.

Published
2014
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63. Electrosynthesis of α-(Silyl)Alkylnitriles

Author

Thierry Constantieux and Jean-Paul Picard

Subjects
Solvent, chemistry.chemical_compound, Silylation, chemistry, Nitrile, Galvanic anode, Organic Chemistry, Organic chemistry, chemistry.chemical_element, Zinc, Electrosynthesis, Anode
Abstract

Sacrificial anode technique has been used to synthetize title compounds in two different ways. First, use was made of α-chloronitriles as the starting materials, zinc as the anode and a THF-HMPA mixture as the solvent. Second, use of an aluminium-made anode, the nitrile being at the same time the substrate and the solvent was shown to be also efficient. This work is part of the Ph.D. Thesis of T.C. (University Bordeaux I, 1994). Present address: Laboratoire de Synthese Asymetrique (URA 1410 CNRS) ENSSPICAM, Faculte des Sciences de Saint-Jerbme, Avenue Nomandie- Nibmen, 13297 Marseille Cedex 20 (France).

Published
1997
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64. Enantioselective palladium catalyzed allylic substitution with new chiral pyridine-phosphine ligands

Author

Gérard Buono, Agnès H. Labande, Jean Michel Brunel, Frédéric Lubatti, and Thierry Constantieux

Subjects
Allylic rearrangement, Organic Chemistry, Substitution (logic), Enantioselective synthesis, chemistry.chemical_element, Biochemistry, Medicinal chemistry, Catalysis, chemistry.chemical_compound, chemistry, Drug Discovery, Pyridine, Organic chemistry, Phosphine, Palladium
Abstract

The synthesis of new chiral pyridine-phosphine ligands 1–3 was achieved and assessed in the enantioselective palladium catalyzed allylic substitution of 1,3-diphenyl-2-propenyl acetate 4 with dimethylmalonate 5 . Enantioselectivities up to 87% were obtained.

Published
1997
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65. ChemInform Abstract: Michael Addition-Initiated Sequential Reactions from 1,3-Dicarbonyls for the Synthesis of Polycyclic Heterocycles

Author

Yoann Coquerel, Thierry Constantieux, Jean Rodriguez, Damien Bonne, and Xavier Bugaut

Subjects
Addition reaction, Chemistry, Michael reaction, General Medicine, Combinatorial chemistry, Domino
Abstract

This review aims to highlight the most significant recent developments on synthetic strategies involving consecutive, domino and multicomponent reactions featuring a Michael addition-initiating step for the synthesis of polycyclic heterocycles from 1,3-dicarbonyls. These original sequences constitute more efficient and eco-compatible alternatives to known synthetic approaches to heterocyclic compounds allowing for an even faster and highly desirable generation of molecular diversity and complexity.

Published
2013
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66. ChemInform Abstract: Metal-Free Michael-Addition-Initiated Three-Component Reaction for the Regioselective Synthesis of Highly Functionalized Pyridines: Scope, Mechanistic Investigations and Applications

Author

Jean Rodriguez, Christophe Allais, Frederic Lieby-Muller, and Thierry Constantieux

Subjects
chemistry.chemical_compound, Scope (project management), Cascade reaction, Metal free, Chemistry, Pyridine, Michael reaction, Regioselectivity, General Medicine, Ring (chemistry), Combinatorial chemistry, Environmentally friendly
Abstract

A metal-free and completely regioselective three-component synthesis of highly functionalized pyridines from 1,3-dicarbonyl derivatives and Michael acceptors has been achieved. Activated Michael acceptors, that is, β,γ-unsaturated α-oxo carbonyl derivatives, were utilized, allowing substitution at the 4-position and remarkable functional diversity at the 2-position of the pyridine ring. The scope and limitations of this environmentally friendly domino reaction are disclosed, with full experimental data, and the results of mechanistic investigations are discussed.

Published
2013
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67. ChemInform Abstract: Activation of 1,2- and 1,3-Ketoamides with Thiourea Organocatalyst for the Enantioselective Domino Synthesis of Functionalized Cyclohexanes

Author

Thierry Constantieux, Maria del Mar Sanchez Duque, Xavier Bugaut, Wilfried Raimondi, Jean Rodriguez, Adrien Quintard, Damien Bonne, and Sébastien Goudedranche

Subjects
chemistry.chemical_classification, chemistry.chemical_compound, chemistry, Thiourea, Bicyclic molecule, Cyclohexanes, Enantioselective synthesis, Organic chemistry, General Medicine, Bridged compounds, Chirality (chemistry), Domino, Stereocenter
Abstract

Several reactive sites of 1,2- and 1,3-ketoamides were successively exploited in two complementary domino transformations for the synthesis of polysubstituted monocyclic or bridged bicyclic cyclohexanes, with the creation of up to six stereogenic centers. In both cases, a chiral bifunctional thiourea organocatalyst allowed efficient control of chirality in the final carbocycle.

Published
2013
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68. ChemInform Abstract: Enantioselective Organocatalyzed Domino Synthesis of Six-Membered Carbocycles

Author

Damien Bonne, Sébastien Goudedranche, Xavier Bugaut, Wilfried Raimondi, Thierry Constantieux, and Jean Rodriguez

Subjects
chemistry.chemical_compound, Chemistry, Cyclohexenes, Cyclohexanes, Enantioselective synthesis, Organic chemistry, Organic synthesis, General Medicine, Domino, Stereocenter
Abstract

Polysubstituted chiral cyclohexanes and cyclohexenes are important building blocks in organic synthesis. From historical and pioneering reports to the most recent accounts, this review focuses on domino enantioselective organocatalytic methodologies that have allowed the control of the relative and absolute configurations of up to six stereogenic centers in the construction of these versatile molecular architectures. 1 Introduction 2 Two-Component Transformations 2.1 Michael-Initiated Domino Reactions with α,β-Unsaturated Carbonyl Compounds 2.2 Michael-Initiated Domino Reactions with Nitroolefins 2.3 Non Michael-Initiated Domino Reactions 3 Multicomponent and Related Transformations 3.1 Pseudo-Three-Component Reactions 3.1.1 Michael-Initiated Domino Reactions with Nitroolefins 3.1.2 Michael-Initiated Domino Reactions with α,β-Unsaturated Carbonyl Compounds 3.2 Consecutive Reactions 3.2.1 Michael-Initiated Domino Reactions with Nitroolefins 3.2.2 Michael-Initiated Domino Reactions with α,β-Unsaturated Carbonyl Compounds 3.3 Multicomponent Reactions 3.3.1 Michael-Initiated Domino Reactions with Nitroolefins 3.3.2 Michael-Initiated Domino Reactions with α,β-Unsaturated Carbonyl Compounds 4 Conclusion

Published
2013
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69. Enantioselective organocatalytic multicomponent synthesis of 2,6-diazabicyclo[2.2.2]octanones

Author

Thierry Constantieux, Jean-Christophe Plaquevent, Xavier Bugaut, Maria del Mar Sanchez Duque, Yves Génisson, Olivier Baslé, Jean Rodriguez, STeRéO, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Synthèse et Physico-Chimie de Molécules d'Intérêt Biologique (SPCMIB), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Yves Génisson et Jean-Christophe Plaquevent (Université Paul Sabatier Toulouse III, CNRS, LSPCMIB UMR 5068 31062 Toulouse (France)), ANR-07-CP2D-0006,CIL-MCRS,Reactions Domino Multicomposés et Liquides Ioniques à Tâches Spécifiques : Nouvelles Approches Eco-Compatibles en Synthèse Organique(2007), Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Octanone, heterocycles, multicomponent reactions, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Acrolein, Enantioselective synthesis, General Medicine, General Chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, 3. Good health, 0104 chemical sciences, Stereocenter, chemistry.chemical_compound, chemistry, Organocatalysis, enantioselectivity, synthetic methods, Organic chemistry, organocatalysis, Amine gas treating, Bifunctional
Abstract

International audience; The title reaction of β-ketoamides, acrolein, and aminophenols, catalyzed by a bifunctional thiourea-tertiary amine organocatalyst, enables the preparation of an enantioenriched diazabicyclo[2.2.2]octanone (2,6-DABCO) scaffold. The chemoselective reaction sequence installs five new bonds and three stereocenters, two of which are contiguous tetrasubstituted centers, with excellent yields and high levels of stereocontrol. M.S.=molecular sieves

Published
2013
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70. ChemInform Abstract: Stereoselective Multiple Bond-Forming Transformations (MBFTs): The Power of 1,2- and 1,3-Dicarbonyl Compounds

Author

Jean Rodriguez, Damien Bonne, Thierry Constantieux, and Yoann Coquerel

Subjects
Ideal (set theory), Computational chemistry, Chemistry, Bond, Stereoselectivity, General Medicine
Abstract

Although long known, 1,2- and 1,3-dicarbonyl compounds have recently come more and more to prevalence as ideal substrates for the invention of new stereoselective multiple bond-forming transformations (MBFTs). Herein, a critical appraisal is presented of some of the most spectacular of these MBFTs, which allow the formation from three up to six bonds in highly step- and atom-economical processes.

Published
2013
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72. Activation of 1,2- and 1,3-Ketoamides with Thiourea Organocatalyst for the Enantioselective Domino Synthesis of Fuctionalized Cyclohexanes

Author

Xavier Bugaut, Wilfried Raimondi, Maria del Mar Sanchez Duque, Adrien Quintard, Jean Rodriguez, Sébastien Goudedranche, Damien Bonne, Thierry Constantieux, STeRéO, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC), and Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)

Subjects
Bicyclic molecule, ketones, catalysis, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, domino reactions, cyclizations, Enantioselective synthesis, cycloalkanes, 010402 general chemistry, stereoselectivity, 01 natural sciences, Combinatorial chemistry, Domino, 0104 chemical sciences, Stereocenter, amides, chemistry.chemical_compound, Thiourea, chemistry, Cyclohexanes, thioureas, Bifunctional, Chirality (chemistry)
Abstract

International audience; Several reactive sites of 1,2- and 1,3-ketoamides were successively exploited in two complementary domino transformations for the synthesis of polysubstituted monocyclic or bridged bicyclic cyclohexanes, with the creation of up to six stereogenic centers. In both cases, a chiral bifunctional thiourea organocatalyst allowed efficient control of chirality in the final carbocycle.

Published
2013
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73. ChemInform Abstract: Enantioselective Organocatalytic Michael Addition of Cyclobutanones to Nitroalkenes

Author

Yoann Coquerel, Maria del Mar Sanchez Duque, Jean Rodriguez, Damien Bonne, Wilfried Raimondi, Damien Mailhol, and Thierry Constantieux

Subjects
Addition reaction, Chemistry, Michael reaction, Enantioselective synthesis, Organic chemistry, Stereoselectivity, General Medicine
Abstract

The organocatalytic, stereoselective Michael-addition of nitroalkenes to functionalized cyclobutanones is presented.

Published
2013
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74. Enamines of Acylsilanes: Electrochemical Synthesis, Structure, and Use as a Source of α-(Trimethylsilyl)alkylamines

Author

Thierry Constantieux and Jean-Paul Picard

Subjects
Inorganic Chemistry, chemistry.chemical_compound, Sodium borohydride, Trimethylsilyl, chemistry, Organic Chemistry, Iminium, Physical and Theoretical Chemistry, Electrochemistry, Medicinal chemistry
Abstract

α-(Trimethylsilyl)alkylamines (“RSMA”), 1, have been prepared with good yields from enamines of acylsilanes, 2, through reduction of the corresponding iminium salts, 5, with sodium borohydride. The...

Published
1996
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75. Synthesis of Furan Atropisomers by Central-to-Axial Chirality Conversion

Author

M Jean, V S Raut, Denis Höfler, Thierry Constantieux, Cyril Bressy, N Vanthuyne, Jean Rodriguez, D. Bonne, Xavier Bugaut, Benjamin List, and C Roussel

Subjects
chemistry.chemical_compound, Atropisomer, Axial chirality, Chemistry, Stereochemistry, Furan, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences
Published
2017
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76. ChemInform Abstract: Expeditious, Metal-Free, Domino, Regioselective Synthesis of Highly Substituted 2-Carbonyl- and 2-Phosphorylfurans by Formal [3 + 2] Cycloaddition

Author

Damien Bonne, Jean Rodriguez, Thierry Constantieux, Daniel Dauzonne, and Wilfried Raimondi

Subjects
Nucleophile, Metal free, Chemistry, Electrophile, Regioselectivity, General Medicine, Combinatorial chemistry, Cycloaddition, Domino
Abstract

2-Functionalized furans are very easily synthesized by exploiting the dual nucleophilic character of 1,2-dicarbonyls and the dual electrophilic properties of (2-chloro-2-nitroethenyl)benzenes in a one-pot, formal [3+2] cycloaddition. Using a base (DBU), the desired trisubstituted heterocycles were formed rapidly (10–30 min) in good to excellent yields (51–92 %), and this versatile, metal-free methodology was applied to the synthesis of 2-acyl- and 2-carboalkoxyfurans and furan-2-carboxamides. Additionally, by using 2-ketophosphonate derivatives as dinucleophiles, the corresponding 2-phosphorylfurans were formed in good yields (53–74 %).

Published
2013
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77. ChemInform Abstract: Dual Heterogeneous Catalysis for a Regioselective Three-Component Synthesis of Bi- and Tri(hetero)arylpyridines

Author

Frederic Lieby‐Muller, Thierry Constantieux, Jean Rodriguez, and Christophe Allais

Subjects
chemistry.chemical_compound, chemistry, Component (thermodynamics), Aryl, Regioselectivity, General Medicine, Heterogeneous catalysis, Ammonium acetate, Combinatorial chemistry, Dual (category theory)
Abstract

The reaction of activated Michael acceptors, 1,3-dicarbonyl derivatives and ammonium acetate allows for the preparation of a library of highly substituted bi- and tri(hetero)aryl pyridines.

Published
2013
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78. ChemInform Abstract: Cooperative Heterogeneous Organocatalysis and Homogeneous Metal Catalysis for the One-Pot Regioselective Synthesis of 2-Pyridones

Author

Jean-Marie Grassot, Olivier Baslé, Thierry Constantieux, Christophe Allais, Stéphane Anguille, Jean Rodriguez, and Maxime Fontaine

Subjects
Metal, Primary (chemistry), Homogeneous, Chemistry, Organocatalysis, visual_art, visual_art.visual_art_medium, Regioselectivity, General Medicine, Combinatorial chemistry, Catalysis
Abstract

An unprecedented formal [3 + 3]-cyclodehydration approach leads to the synthesis of N-alkyl and N-arylsubstituted 2-pyridones from β-ketoamides and primary or secondary propargylic alcohols.

Published
2013
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79. Stereoselective Multiple Bond-Forming Transformations (MBFTs): The Power of 1,2- and 1,3-Dicarbonyl Compounds

Author

Jean Rodriguez, Damien Bonne, Thierry Constantieux, Yoann Coquerel, STeRéO, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC), and Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Ideal (set theory), 010405 organic chemistry, Chemistry, multicomponent reactions, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Bond, Organic Chemistry, domino reactions, General Chemistry, 010402 general chemistry, diastereoselectivity, 01 natural sciences, Catalysis, 0104 chemical sciences, carbonyl compounds, Computational chemistry, enantioselectivity, Organic chemistry, Stereoselectivity
Abstract

International audience; Although long known, 1,2- and 1,3-dicarbonyl compounds have recently come more and more to prevalence as ideal substrates for the invention of new stereoselective multiple bond-forming transformations (MBFTs). Herein, a critical appraisal is presented of some of the most spectacular of these MBFTs, which allow the formation from three up to six bonds in highly step- and atom-economical processes.

Published
2013
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80. ChemInform Abstract: Asymmetric Organocascades Involving the Formation of Two C-Heteroatom Bonds from Two Distinct Heteroatoms

Author

Damien Bonne, Jean Rodriguez, Yoann Coquerel, and Thierry Constantieux

Subjects
Chemistry, Organocatalysis, Heteroatom, Enantioselective synthesis, General Medicine, Optically active, Combinatorial chemistry, Domino
Abstract

In the vast and expanding world of enantioselective organocascades, the ones in which two C–heteroatom bonds are created from two distinct heteroatoms are rare. These fascinating domino processes constitutes real synthetic challenges and allow very convenient syntheses of diverse optically active heterocycles and also highly functionalised acyclic derivatives.

Published
2012
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81. Cooperative Heterogeneous Organocatalysis and Homogeneous Metal Catalysis for the One-Pot Regioselective Synthesis of 2-Pyridones

Author

Olivier Baslé, Christophe Allais, Jean-Marie Grassot, Jean Rodriguez, Maxime Fontaine, Stéphane Anguille, Thierry Constantieux, STeRéO, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC), ANR-07-CP2D-0006,CIL-MCRS,Reactions Domino Multicomposés et Liquides Ioniques à Tâches Spécifiques : Nouvelles Approches Eco-Compatibles en Synthèse Organique(2007), and Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Primary (chemistry), 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Oxide, Regioselectivity, General Chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Catalysis, Metal, propargylic alcohol, chemistry.chemical_compound, Transition metal, chemistry, Homogeneous, Organocatalysis, visual_art, visual_art.visual_art_medium, Organic chemistry, beta-keto-amides, Cooperative catalysis, organocatalysis, 2-pyridones
Abstract

International audience; A direct, one-pot and regioselective access to N-alkyl- and N-aryl-substituted 2-pyridones is described from readily available β-ketoamides and either primary or secondary propargyl alcohols. This approach involves the combination of two different cooperative homogeneous and heterogeneous catalytic systems based on a transition metal oxide and a supported organocatalyst, respectively.

Published
2012
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82. ChemInform Abstract: Activation of 1,2-Keto Esters with Takemoto′s Catalyst Toward Michael Addition to Nitroalkenes

Author

Jean Rodriguez, Damien Bonne, Olivier Baslé, Wilfried Raimondi, and Thierry Constantieux

Subjects
chemistry.chemical_compound, Thiourea, Chemistry, Michael reaction, Organic chemistry, General Medicine, Catalysis
Abstract

The use of the chiral thiourea catalyst provides the addition products with < 90% antiselectivity and up to 98% enantioselectivity.

Published
2012
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83. Activation of 1,2-Keto Esters with Takemoto's Catalyst toward Michael Addition to Nitroalkenes

Author

Damien Bonne, Wilfried Raimondi, Olivier Baslé, Thierry Constantieux, Jean Rodriguez, STeRéO, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC), and Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, organic chemicals, education, asymmetric organocatalysis, Takemoto's catalyst, General Chemistry, Optically active, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, 3. Good health, Catalysis, pronucleophiles, Nucleophile, Michael addition, Michael reaction, 2-keto esters, Organic chemistry, heterocyclic compounds, Enantiomer
Abstract

International audience; When activated with Takemoto's catalyst, 1,2-keto esters constitute versatile nucleophiles in the Michael addition reaction with nitroalkenes affording synthetically valuable, optically active anti-adducts in very good yields and high enantiomeric excesses.

Published
2012
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84. Reductive Electrochemical Silylation of Unsaturated Nitrogen Functionalities: A Simple and Efficient Synthesis of Precursors of Bis(trimethylsilyl)methylamine

Author

Jesus Maria Aizpurua, Stéphane Grelier, Claudio Palomo, Michel Bordeau, Denis Deffieux, Jacques Dunogues, Jean-Paul Picard, and Thierry Constantieux

Subjects
Inorganic Chemistry, chemistry.chemical_compound, Trimethylsilyl, chemistry, Silylation, Methylamine, Organic Chemistry, Chemical reduction, Organic chemistry, chemistry.chemical_element, Physical and Theoretical Chemistry, Electrochemistry, Nitrogen
Published
1994
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85. ChemInform Abstract: Multicomponent Reactions in Ionic Liquids: Convenient and Ecocompatible Access to the 2,6-DABCO Core

Author

Frédéric Guillen, Thierry Constantieux, Zhor El Asri, Jean-Christophe Plaquevent, Maria del Mar Sanchez Duque, Nicolas Isambert, Sonia Ladeira, Yves Génisson, Olivier Baslé, and Jean Rodriguez

Subjects
Solvent, chemistry.chemical_compound, chemistry, Computational chemistry, Ionic liquid, Core (manufacturing), General Medicine, DABCO, Heterogeneous catalysis, Molecular sieve, Toluene, Octane
Abstract

Herein we describe the use of ionic liquids as complementary new media for multicomponent reactions leading to the 2,6-diazabicyclo[2.2.2]octane core. The reaction took place efficiently in ionic liquid solvents instead of toluene, giving overall better results (faster rate, higher concentration) and allowing generalization to hitherto unreactive substituted Michael acceptors. In these cases, the use of molecular sieves, acting as a heterogeneous catalyst in the preliminary study in molecular solvents, could be totally excluded thanks to the promoting properties of the ionic liquid solvent, which could be recycled and reused up to five times. Complete diastereoselectivity was observed at one of the bridge positions, as assigned by X-ray analysis.

Published
2011
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86. ChemInform Abstract: A Cooperative Participation of the Amido Group in the Organocatalytic Construction of All-Carbon Quaternary Stereocenters by Michael Addition with β-Ketoamides

Author

Olivier Basle, Jean Rodriguez, Anouk Gaudel-Siri, Thierry Constantieux, Jean-Christophe Plaquevent, Maria del Mar Sanchez Duque, Yves Genisson, and Nicolas Isambert

Subjects
chemistry, Stereochemistry, Group (periodic table), Michael reaction, chemistry.chemical_element, General Medicine, Ethylvinylketone, Carbon, Stereocenter
Abstract

The novel organocatalytic reaction of cyclic α-substituted β-ketoamides to methyl- or ethylvinylketone proceeds with high yields and enantioselectivities to afford the products bearing all-carbon quaternary stereocenter [cf.

Published
2011
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87. Multicomponent reactions in ionic liquids: convenient and ecocompatible access to the 2,6-DABCO core

Author

Jean-Christophe Plaquevent, Maria del Mar Sanchez Duque, Olivier Baslé, Sonia Ladeira, Frédéric Guillen, Nicolas Isambert, Yves Génisson, Jean Rodriguez, Zhor El Asri, Thierry Constantieux, Synthèse et Physico-Chimie de Molécules d'Intérêt Biologique (SPCMIB), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), STeRéO, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Paul Sabatier - Toulouse III, ANR-07-CP2D-0006,CIL-MCRS,Reactions Domino Multicomposés et Liquides Ioniques à Tâches Spécifiques : Nouvelles Approches Eco-Compatibles en Synthèse Organique(2007), Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Multicomponent, DABCO, 010402 general chemistry, Heterogeneous catalysis, Molecular sieve, 01 natural sciences, Pollution, Toluene, 0104 chemical sciences, Solvent, chemistry.chemical_compound, chemistry, Computational chemistry, Michael addition, Ionic liquid, β-ketoamide, Michael reaction, Environmental Chemistry, Organic chemistry, Octane, ionic liquid
Abstract

International audience; Herein we describe the use of ionic liquids as complementary new media for multicomponent reactions leading to the 2,6-diazabicyclo[2.2.2]octane core. The reaction took place efficiently in ionic liquid solvents instead of toluene, giving overall better results (faster rate, higher concentration) and allowing generalization to hitherto unreactive substituted Michael acceptors. In these cases, the use of molecular sieves, acting as a heterogeneous catalyst in the preliminary study in molecular solvents, could be totally excluded thanks to the promoting properties of the ionic liquid solvent, which could be recycled and reused up to five times. Complete diastereoselectivity was observed at one of the bridge positions, as assigned by X-ray analysis.

Published
2011
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88. ChemInform Abstract: Multicomponent Reactions and Ionic Liquids: A Perfect Synergy for Eco-Compatible Heterocyclic Synthesis

Author

Jean-Christophe Plaquevent, Jean Rodriguez, Maria del Mar Sanchez Duque, Yves Génisson, Nicolas Isambert, and Thierry Constantieux

Subjects
Green chemistry, chemistry.chemical_compound, Chemistry, Yield (chemistry), Ionic liquid, Combined use, General Medicine, Biochemical engineering, Raw material, Energy requirement, Chemical synthesis, Catalysis
Abstract

The efficiency of a chemical synthesis can be nowadays measured, not only by parameters like selectivity and overall yield, but also by its raw material, time, human resources and energy requirements, as well as the toxicity and hazard of the chemicals and the protocols involved. The development of multicomponent reactions (MCRs) in the presence of task-specific ionic liquids (ILs), used not only as environmentally benign reaction media, but also as catalysts, is a new approach that meet with the requirements of sustainable chemistry. The aim of this tutorial review is to highlight the synergistic effect of the combined use of MCRs and ILs for the development of new eco-compatible methodologies for heterocyclic chemistry.

Published
2011
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89. ChemInform Abstract: Highly Diastereo- and Enantioselective Organocatalytic Michael Addition of α-Ketoamides to Nitroalkenes

Author

Olivier Basle, Maria del Mar Sanchez Duque, Damien Bonne, Wilfried Raimondi, Jean Rodriguez, and Thierry Constantieux

Subjects
body regions, Chemistry, fungi, education, Enantioselective synthesis, Michael reaction, Organic chemistry, General Medicine, Selectivity, behavioral disciplines and activities, humanities, Adduct
Abstract

The method furnishes Michael adducts with high anti selectivity (

Published
2011
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90. ChemInform Abstract: β-Diketo Building Blocks for MCRs-Based Syntheses of Heterocycles

Author

Christophe Allais, Jean Rodriguez, Nicolas Isambert, Maria del Mar Sanchez Duque, and Thierry Constantieux

Subjects
Primary (chemistry), Chemistry, Context (language use), General Medicine, Combinatorial chemistry, Organic molecules
Abstract

In the context of sustainable chemistry, because of economic and ecological increasing pressure, domino multicomponent reactions (MCRs) constitute a central academic and industrial investigation domain in diversity-oriented synthesis of functionalized heterocycles. Although isocyanide-based MCRs generally predominate nowadays, the use of 1,3-dicarbonyls as substrates, proposed as early as 1882 by Hantzsch, proved to be highly efficient, but have been relatively unexplored until recently. In the last few years, such transformations received a growing attention as new useful methodologies valuable for the selective direct access to highly functionalized small organic molecules of primary synthetic and biological value. This review focuses on the more significant recent developments on the use of β-diketo building blocks for MCRs published in the last 5 years.

Published
2011
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91. A cooperative participation of the amido group in the organocatalytic construction of all-carbon quartenary stereocenters by Michael addition with beta-ketoamides

Author

Yves Genisson, Nicolas Isambert, Maria del Mar Sanchez Duque, Jean Rodriguez, Anouk Gaudel-Siri, Thierry Constantieux, Jean-Christophe Plaquevent, Olivier Basle, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-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), Centre Régional de Lutte contre le cancer Georges-François Leclerc [Dijon] (UNICANCER/CRLCC-CGFL), UNICANCER, Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Synthèse et Physico-Chimie de Molécules d'Intérêt Biologique (SPCMIB), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), STeRéO, Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Université Paul Sabatier (Toulouse III), ANR-07-CP2D-06,CP2D,Reactions Domino Multicomposés et Liquides Ioniques à Tâches Spécifiques : Nouvelles Approches Eco-Compatibles en Synthèse Organique(2007), 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), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Stereochemistry, spiro compounds, beta-ketoamide, chemistry.chemical_element, alpha-hydroxy lactam, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, Stereocenter, Group (periodic table), Michael addition, Reactivity (chemistry), organocatalysis, Physical and Theoretical Chemistry, Molecular Structure, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Hydrogen Bonding, Stereoisomerism, Amides, Carbon, 0104 chemical sciences, Bifunctional catalyst, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry, Organocatalysis, Michael reaction, bifunctional catalyst, Selectivity
Abstract

International audience; The secondary amido group of α-substituted β-ketoamides plays a crucial role in the control of the reactivity and spatial arrangement (selectivity) in the organocatalyzed Michael addition to unsaturated carbonyls. This results in an unprecedented activation mode of substrates through H-bonding interactions allowing the construction of enantiomerically enriched functionalized all-carbon quaternary centers and spiroaminals of high synthetic potential.

Published
2011
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92. Bis(trimethylsilyl)methylamine from cyanides

Author

Jesus Maria Aizpurua, Claudio Palomo, Jean-Michel Léger, Stéphane Grelier, Jean Paul Picard, Thierry Constantieux, Jacques Dunogues, Ludovico Lunazzi, Michel Pétraud, and Bernard Barbe

Subjects
Reaction mechanism, Trimethylsilyl, Methylamine, Organic Chemistry, chemistry.chemical_element, Nuclear magnetic resonance spectroscopy, Medicinal chemistry, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Chemical reduction, Organic chemistry, Lithium, Physical and Theoretical Chemistry
Published
1993
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93. ChemInform Abstract: 1,3-Dicarbonyl Compounds in Stereoselective Domino and Multicomponent Reactions

Author

Damien Bonne, Thierry Constantieux, Jean Rodriguez, and Yoann Coquerel

Subjects
Green chemistry, chemistry.chemical_compound, chemistry, Covalent bond, Functional group, Organic chemistry, Molecule, Stereoselectivity, Organic synthesis, Context (language use), General Medicine, Combinatorial chemistry, Domino
Abstract

Modern organic synthesis focuses on the discovery and the development of stereoselective multiple bond-forming transformations allowing the creation of several covalent bonds in a single operation. Hence, the number of steps required to obtain a target molecule is reduced, which nicely addresses the efficiency and economy criteria of ‘green chemistry’. In this context, 1,3-dicarbonyl compounds are exceptional synthetic platforms due to the presence of four contiguous reaction sites. This functional group density allows cascades of elemental steps from simple substrates leading to the selective formation of elaborated molecular architectures displaying a large functional diversity.

Published
2010
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94. Highly diastereo- and enantioselective organocatalytic Michael addition of alpha-ketoamides to nitroalkenes

Author

Wilfried Raimondi, Damien Bonne, Maria del Mar Sanchez Duque, Jean Rodriguez, Olivier Basle, Thierry Constantieux, STeRéO, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC), ANR-07-CP2D-0006,CIL-MCRS,Reactions Domino Multicomposés et Liquides Ioniques à Tâches Spécifiques : Nouvelles Approches Eco-Compatibles en Synthèse Organique(2007), and Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Cyclohexane, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Enantioselective synthesis, Substrate (chemistry), 010402 general chemistry, 01 natural sciences, Biochemistry, 0104 chemical sciences, Catalysis, alphaa-ketoamide, chemistry.chemical_compound, Cascade reaction, chemistry, Thiourea, Nitroalkenes, Michael addition, Michael reaction, bifunctional catalyst, Organic chemistry, organocatalysis, Physical and Theoretical Chemistry, Bifunctional
Abstract

International audience; The first organocatalytic enantio- and diastereoselective conjugate addition of r-ketoamides to nitroalkenes has been achieved using a bifunctional amino thiourea catalyst. In this new approach, the substrate amide proton plays a critical role in the formation of the Michael anti-adducts in high yields and high stereoselectivities. To illustrate the high synthetic potential of this methodology, the diastereo- and enantioselective synthesis of a hexasubstituted cyclohexane via a Michael-Michael-Henry cascade reaction is described.

Published
2010
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95. ChemInform Abstract: Fluoride Ion-Mediated Peterson Alkenation of N-(C,C-Bis(trimethylsilyl) methyl)amido Derivatives with Carbonyl Compounds: A Short General Route to Enamides and 1,2-Dihydroisoquinolines

Author

J. Dunogues, Jesus M. Aizpurua, Jean Paul Picard, Thierry Constantieux, Claudio Palomo, and Marta Legido

Subjects
chemistry.chemical_compound, chemistry, Trimethylsilyl, Methylamine, Organic chemistry, General Medicine, Fluoride, Peterson olefination, Ion
Abstract

A straightforward general access to diversely substituted acyclic or cyclic enamides and dienamides is accomplished by using a fluoride induced Peterson olefination of carbonyl compounds and enolizable amides derived from C,C-bis(trimethylsilyl) methylamine.

Published
2010
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97. ChemInform Abstract: Enamines of Acylsilanes: Electrochemical Synthesis, Structure, and Use as a Source of α-(Trimethylsilyl)alkylamines

Author

Thierry Constantieux and Jean-Paul Picard

Subjects
chemistry.chemical_compound, Sodium borohydride, Trimethylsilyl, chemistry, Iminium, Organic chemistry, General Medicine, Electrochemistry
Abstract

α-(Trimethylsilyl)alkylamines (“RSMA”), 1, have been prepared with good yields from enamines of acylsilanes, 2, through reduction of the corresponding iminium salts, 5, with sodium borohydride. The...

Published
2010
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98. ChemInform Abstract: Enantioselective Palladium Catalyzed Allylic Substitution with New Chiral Pyridine-Phosphine Ligands

Author

Agnès H. Labande, Jean Michel Brunel, Thierry Constantieux, Gérard Buono, and Frédéric Lubatti

Subjects
Substitution reaction, Allylic rearrangement, chemistry.chemical_compound, Chemistry, Pyridine, Substitution (logic), Enantioselective synthesis, chemistry.chemical_element, General Medicine, Medicinal chemistry, Phosphine, Palladium, Catalysis
Abstract

The synthesis of new chiral pyridine-phosphine ligands 1–3 was achieved and assessed in the enantioselective palladium catalyzed allylic substitution of 1,3-diphenyl-2-propenyl acetate 4 with dimethylmalonate 5 . Enantioselectivities up to 87% were obtained.

Published
2010
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99. ChemInform Abstract: Electrosynthesis of α-(Silyl)alkylnitriles

Author

Jean-Paul Picard and Thierry Constantieux

Subjects
Solvent, chemistry.chemical_compound, Silylation, Nitrile, Galvanic anode, Chemistry, Polymer chemistry, chemistry.chemical_element, General Medicine, Zinc, Electrosynthesis, Anode
Abstract

Sacrificial anode technique has been used to synthetize title compounds in two different ways. First, use was made of α-chloronitriles as the starting materials, zinc as the anode and a THF-HMPA mixture as the solvent. Second, use of an aluminium-made anode, the nitrile being at the same time the substrate and the solvent was shown to be also efficient. This work is part of the Ph.D. Thesis of T.C. (University Bordeaux I, 1994). Present address: Laboratoire de Synthese Asymetrique (URA 1410 CNRS) ENSSPICAM, Faculte des Sciences de Saint-Jerbme, Avenue Nomandie- Nibmen, 13297 Marseille Cedex 20 (France).

Published
2010
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