Gaultier, Laetitia (2005) From isocyanides to pyruvamides: New developpements of Ugi and phospha-Brook reactions. PhD thesis ENSTA, ENSTA, EP/X p.229.
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Alternative Locations: http://www.imprimerie.polytechnique.fr/Theses/Files/Gaultier.pdf
Abstract
A great part of this thesis is dedicated to chemistry of isocyanides: thus several chapters treat interactions between isocyanides and acids derivatives, a significant part was devoted there to the valorization of the fluorinated pyruvamides obtained by addition of isocyanides on trifluor!
oacetic anhydride . It was thus possible to show the interest of the hydrates of trifluoropyruvamides as a electrophiles with respect to ketones and nitrated derivatives. Pinacolic attempts couplings of pyruvamides thereafter involved us towards the study of a very original aromatic aldehyde reduction by the dimethylphosphite. The mechanism probably implies a Phospha-Brook type rearrangement with direct benzylic phosphate formation. Some synthetic applications of this reaction were tested before reconsidering the chemistry of isocyanides. We could combine a Ugi type reaction with a cyclization of N-acyliminium in a very short synthesis of tricyclic diketopiperazines . This work already led to the publication of three communications, several projects initiated in this thesis will be continued, the coupling between the chemistry of isonitriles and cyclizations of N-acylimminiums seeming particularly promising.
| Item Type: | PhD Thesis (PhD) |
|---|---|
| Thesis Supervisor: | El kaim, Laurent |
| Date: | December 2005 |
| Board of examiners: | Aubert, Corinne and Fouquet, Eric and El kaim, Laurent and Meyer, Christophe and Crousse, Benoit |
| Ecole Doctorale: | ED 447 ECOLE DOCTORALE DE L'ECOLE POLYTECHNIQUE |
| Discipline: | ENSTA |
| Collection (Fonds): | EP/X |
| Institution: | EP/X |
| Department: | ENSTA |
| Subjects: | 6. Chemistry, Physical Chemistry and Chemical Engineering |
| Uncontrolled Keywords: | Isocyanide, Multicomponent, Ugi, Phospha-brook, Phosphate, Diketopiperazine, N-acyliminium, Isonitrile, Multicomposant, Ugi, Phospha-brook, Phosphate, Dicétopipérazine, N-acyliminium |
Table of content
A. INTRODUCTION GENERALE - 7
B. LES ISONITRILES - 11
1. Introduction - 11
2. Abondance naturelle et propriétés biologiques - 11
3. Historique de synthèse - 12
4. Méthodes de préparation des isonitriles - 15
5. Chimie des isonitriles - 18
C. CHLORURE DIMIDOYLE ET REARRANGEMENT DE CHAPMAN - 32
1. La réaction de Nef - 34
2. Le réarangement de Chapman / Overman - 36
a. Chapman - 36
b. Overman - 39
3. Premier essai - 39
4. Mise au point de la formation du chlorure dimidoyle - 40
D. INTRODUCTION PYRUVAMIDES - 47
E. LES TRICHLOROPYRUVAMIDES - 48
1. Synthèse: premiers essais, optimisation et quelques applications - 48
2. Valorisation: addition de nucléophiles - 49
F. LES TRIFLUOROPYRUVAMIDES - 51
1. Importance des produits fluorés et trifluorés en particulier - 51
2. Additions nucléophiles sur les trifluoro-pyruvamides - 56
3. Additions dautres nucléophiles - 80
4. Conclusion sur laddition de nucléophiles - 94
G. REDUCTION DE CARBONYLES PAR LE DIMETHYLPHOSPHITE - 115
1. Bibliographie - 115
2. Optimisation - 121
3. Applications - 123
4. Conclusion sur la Phospha-Brook - 127
5. Valorisation - 128
6. Conclusion sur la valorisation - 139
H. UGI SUR ACIDES CETOCARBOXYLIQUES - 143
1. Introduction - 143
2. Bibliographie - 143
3. Mise au point des conditions expérimentales - 150
4. Etude et formation de dicétopipérazines - 152
5. Applications - 168
6. Conclusion et perspectives - 171
I. CONCLUSION - 175
J. PARTIE EXPERIMENTALE - 179
K. ANNEXES - 273
| ID Code: | 1908 |
|---|---|
| Deposited By: | Laurence Vidament |
| Deposited On: | 15 September 2006 |
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