| Titre : |
Green construction of fused heterocycles & synthesis of carbo-benzenic phosphine derivatives |
| Titre original : |
Construction d'hétérocycles condensés par chimie verte & synthèse de dérivés de phosphines carbo-benzéniques |
| Type de document : |
texte imprimé |
| Auteurs : |
Zhenyu Yao, Auteur ; Remi Chauvin, Directeur de thèse ; Cui, Xinjiang, Directeur de thèse |
| Langues : |
Anglais (eng) |
| Tags : |
BENZO-N-HETEROCYCLES PHOTOCATALYSIS BENZOXAZOLES CS2AGBIBR6 PEROVSKITE NCS PHOSPHINO-PHOSPHONIUM YLIDES CARBO-BENZENE |
| Résumé : |
"Benzo-N-heterocycles, such as benzoxazoles, benzimidazoles, benzothiazoles, and pyrroloquinoxalines are known for their biological activities and widespread use in organic optoelectronics, biochemical analysis, detection, and cell microscopic imaging. The development of new methods for the synthesis of benzo-N-heterocycles is thus of great significance. This thesis mainly addresses the application of Ag-Bi dual perovskite materials for the synthesis of benzo-N-heterocycles under visible light catalysis, but also the use of phosphine-phosphonium ylide ligands in palladium-catalyzed coupling reactions for the same objective, and finally the design and synthesis of a new type of candidate ligands, i.e. carbo-benzenic phosphine derivatives. Perovskites have found applications in numerous domains. Indeed, perovskites have excellent photo-generated charge carrier separation and transport properties, thus showing promising potential in the field of photocatalysis. Chapters 2-4 of this thesis present the preparation of Cs2AgBiBr6 double perovskite nanocrystals (NCs) by anti-solvent recrystallization, and their application to the synthesis of benzo-N-heterocyclic compounds through oxidative condensation processes. In the presence of such photocatalyst, benzimidazoles, benzothiazoles and pyrroloquinoxalines are shown to be synthesized with TON values of 9 million, 5.8 million and 3.6 million, respectively. This method proceeds smoothly under low-power blue LED irradiation using air dioxygen as an oxidant. Mechanistic studies demonstrate that Cs2AgBiBr6 NCs have a suitable conduction band to drive the oxidation of the condensation intermediate. Transition-metal-catalyzed direct C-H bond activation can be regarded as atom-economical and friendly-environmental, but only under the condition of high catalyst efficiency, broad scope of compatible substrates, low reaction temperatures and high yields. For this purpose, ligands play the central role of “chemical hands” for influencing the bond-making and -breaking processes that occur at metal centers. In Chapter 5, phosphino-phosphonium ylides are envisaged as novel bidentate electron-rich P,C-ligands for palladium-catalyzed cross-coupling of benzoxazoles with halo-aromatics. It was found that such ligands allow decreasing the reaction temperature as compared to conventional methods. A series of 2-arylbenzoxazoles has thus been constructed under relatively mild conditions, with broad prospects of applications. Carbo-mers are carbon-rich and π-electron-rich molecules formally obtained by inserting C2 units into each bond of a given parent Lewis structure. Ring carbo-benzenes are thus devised by inserting a C2 unit into each C-C bond of the C6 ring of benzene derivatives, thus making a C18 aromatic ring. This formal process has suggested systematic investigations of carbo-benzene properties, in molecular conductivity, catalyst photosensitization, charge transport (organic photovoltaics), non-linear optics (two photon absorption), and liquid crystal design. In spite of versatile developments in carbo-benzene chemistry, no example featuring a bond between the C18 ring and a heteroatom has ever been reported (all known carbo-benzenes contain C18-H and C18-C bonds only). The challenge is resumed in Chapter 6, where the synthesis of the first carbo-benzene with C18-P bonds is reported, namely the tetraphenyl ring carbo-mer of p-diphenylphosphino-benzene dioxide, through a key [6]pericyclynedione. Beyond p-(Ph2P(O))2C18Ph4, the homologous carbo-benzene p-(Ph2P(O)CH2)2C18Ph4, with C18-C bonds only, is also reported. The synthesis of the carbo-quinoid derivative p-(Ph2P(O)CH)2C18Ph4 is also envisaged. A series of 1,2- and 1,4-addition products of various phosphorus nucleophiles to a dialkynyl-mono-ketone model of the [6]pericyclynedione is also described. Preliminary results of DFT calculations of p-bis(diphenylphosphinoyl)-tetraphenyl-carbo-benzene are also provided." |
| Document : |
Thèse de Doctorat |
| Etablissement_delivrance : |
Université Toulouse 3 en cotutelle avec Huaqiao University |
| Date_soutenance : |
21/11/2023 |
| Ecole_doctorale : |
Sciences de la Matière (SdM) (Toulouse) |
| Domaine : |
Chimie moléculaire |
| En ligne : |
https://theses.fr/s295541 |
Green construction of fused heterocycles & synthesis of carbo-benzenic phosphine derivatives = Construction d'hétérocycles condensés par chimie verte & synthèse de dérivés de phosphines carbo-benzéniques [texte imprimé] / Zhenyu Yao, Auteur ; Remi Chauvin, Directeur de thèse ; Cui, Xinjiang, Directeur de thèse . - [s.d.]. Langues : Anglais ( eng)
| Tags : |
BENZO-N-HETEROCYCLES PHOTOCATALYSIS BENZOXAZOLES CS2AGBIBR6 PEROVSKITE NCS PHOSPHINO-PHOSPHONIUM YLIDES CARBO-BENZENE |
| Résumé : |
"Benzo-N-heterocycles, such as benzoxazoles, benzimidazoles, benzothiazoles, and pyrroloquinoxalines are known for their biological activities and widespread use in organic optoelectronics, biochemical analysis, detection, and cell microscopic imaging. The development of new methods for the synthesis of benzo-N-heterocycles is thus of great significance. This thesis mainly addresses the application of Ag-Bi dual perovskite materials for the synthesis of benzo-N-heterocycles under visible light catalysis, but also the use of phosphine-phosphonium ylide ligands in palladium-catalyzed coupling reactions for the same objective, and finally the design and synthesis of a new type of candidate ligands, i.e. carbo-benzenic phosphine derivatives. Perovskites have found applications in numerous domains. Indeed, perovskites have excellent photo-generated charge carrier separation and transport properties, thus showing promising potential in the field of photocatalysis. Chapters 2-4 of this thesis present the preparation of Cs2AgBiBr6 double perovskite nanocrystals (NCs) by anti-solvent recrystallization, and their application to the synthesis of benzo-N-heterocyclic compounds through oxidative condensation processes. In the presence of such photocatalyst, benzimidazoles, benzothiazoles and pyrroloquinoxalines are shown to be synthesized with TON values of 9 million, 5.8 million and 3.6 million, respectively. This method proceeds smoothly under low-power blue LED irradiation using air dioxygen as an oxidant. Mechanistic studies demonstrate that Cs2AgBiBr6 NCs have a suitable conduction band to drive the oxidation of the condensation intermediate. Transition-metal-catalyzed direct C-H bond activation can be regarded as atom-economical and friendly-environmental, but only under the condition of high catalyst efficiency, broad scope of compatible substrates, low reaction temperatures and high yields. For this purpose, ligands play the central role of “chemical hands” for influencing the bond-making and -breaking processes that occur at metal centers. In Chapter 5, phosphino-phosphonium ylides are envisaged as novel bidentate electron-rich P,C-ligands for palladium-catalyzed cross-coupling of benzoxazoles with halo-aromatics. It was found that such ligands allow decreasing the reaction temperature as compared to conventional methods. A series of 2-arylbenzoxazoles has thus been constructed under relatively mild conditions, with broad prospects of applications. Carbo-mers are carbon-rich and π-electron-rich molecules formally obtained by inserting C2 units into each bond of a given parent Lewis structure. Ring carbo-benzenes are thus devised by inserting a C2 unit into each C-C bond of the C6 ring of benzene derivatives, thus making a C18 aromatic ring. This formal process has suggested systematic investigations of carbo-benzene properties, in molecular conductivity, catalyst photosensitization, charge transport (organic photovoltaics), non-linear optics (two photon absorption), and liquid crystal design. In spite of versatile developments in carbo-benzene chemistry, no example featuring a bond between the C18 ring and a heteroatom has ever been reported (all known carbo-benzenes contain C18-H and C18-C bonds only). The challenge is resumed in Chapter 6, where the synthesis of the first carbo-benzene with C18-P bonds is reported, namely the tetraphenyl ring carbo-mer of p-diphenylphosphino-benzene dioxide, through a key [6]pericyclynedione. Beyond p-(Ph2P(O))2C18Ph4, the homologous carbo-benzene p-(Ph2P(O)CH2)2C18Ph4, with C18-C bonds only, is also reported. The synthesis of the carbo-quinoid derivative p-(Ph2P(O)CH)2C18Ph4 is also envisaged. A series of 1,2- and 1,4-addition products of various phosphorus nucleophiles to a dialkynyl-mono-ketone model of the [6]pericyclynedione is also described. Preliminary results of DFT calculations of p-bis(diphenylphosphinoyl)-tetraphenyl-carbo-benzene are also provided." |
| Document : |
Thèse de Doctorat |
| Etablissement_delivrance : |
Université Toulouse 3 en cotutelle avec Huaqiao University |
| Date_soutenance : |
21/11/2023 |
| Ecole_doctorale : |
Sciences de la Matière (SdM) (Toulouse) |
| Domaine : |
Chimie moléculaire |
| En ligne : |
https://theses.fr/s295541 |
|  |
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