Charrier, Nicolas (2008) New radical allylation reactions. PhD thesis DCSO, DCSO, EP/X p.365.
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Abstract
Over the past decades, we have developed a powerful carbon-carbon bond formation process based on xanthate radical chemistry. The dithiocarbonate group is transferred on the product at the end of the process. In these studies, we showed that, instead of being a drawback, this transfer was a very good starting point to perform radical allylation reactions. The first method is based on α-substituted allylsulfones. Unlike allylstannanes, allyl isopropylsulfones are a very good allylating agent, showing no traces of isomerized starting olefine. Thanks to this method, skipped dienes and enynes were very conveniently introduced on various compounds. The system triethylborane/oxygen proved to be a very powerful initiating system to do additions of various xanthates onto vinyl epoxides at room temperature. Allylic alcohols were formed in very mild conditions as well as allyl amines and allenic alcohols. A radical equival!
ent of the Wittig reaction has been developed using fluoropyridine ethers. Addition of vinylmagnesium bromide on various ketones and aldehydes and substitution of 2,6-difluoropyridine by the corresponding alcolates led to the formation of very powerful allylating agents. Various compounds, such as an amino acid bearing a sugar on its side chain, were successfully prepared. Finally, 5-arylpiperidin-2-ones were synthesized by a radical process based on the cyclisation on aniline derivatives. The piperidinones and their bicyclic precursors could have interesting biological properties. As a consequence, we have shown over those four studies all the richness and the potential of radical based xanthate chemistry.
| Item Type: | PhD Thesis (PhD) |
|---|---|
| PhD Supervisor: | Zard, Samir |
| Date: | 20 October 2008 |
| Board of examiners: | Kouklovsky, Cyrille and Renaud, Philippe and Micouin, Laurent and Demont, Emmanuel and Zard, Samir |
| Ecole Doctorale: | ED 447 ECOLE DOCTORALE DE L'ECOLE POLYTECHNIQUE |
| Discipline: | DCSO |
| Collection (Fonds): | Ecole Polytechnique (EP/X) |
| Institution: | EP/X |
| Department: | DCSO |
| Subjects: | 6. Chemistry, Physical Chemistry and Chemical Engineering |
| Uncontrolled Keywords: | Radical chemistry, Xanthates, Allylation, Sulfones, Vinyl epoxides, Fluoropyrdine, Piperidinone, Triethylborane, Chimie radicalaire, Xanthates, Allylation, Sulfones, Epoxydes vinyliques, Fluoropyridine, Pipéridinone, Triéthylborane |
| ID Code: | 4272 |
| Deposited By: | Laurence Vidament |
| Deposited On: | 23 October 2008 |
Table of content
Introduction générale - 23
Chapitre I : La chimie radicalaire par propagation de chaîne - 27
I. Principes de la chimie radicalaire par propagation de chaîne - 30
II. Méthodes de chimie radicalaire par propagation de chaîne - 32
III. Conclusion - 36
Chapitre II : La chimie radicalaire des xanthates - 39
I. Quelques aspects de la chimie ionique des xanthates - 41
II. Réaction de Barton-McCombie - 42
III. Principe de la chimie radicalaire par transfert de groupe - 46
IV. Préparation des xanthates - 49
V. Illustration du potentiel synthétique de la chimie radicalaire des xanthates - 53
VI. Conclusion - 63
Chapitre III : Les allylations radicalaires - 65
I. Généralités - 68
II. Les dérivés de létain - 69
III. Dérivés du soufre - 80
IV. Dérivés du silicium - 91
V. Les halogénures allyliques - 93
VI. Autres dérivés - 94
VII. Conclusion - 96
Chapitre IV : Allylations radicalaires basées sur des allyles sulfones substituées - 99
I. A la source de nos travaux - 101
II. Allylations utilisant des agents tolérants la substitution en position 1 - 102
III. Utilisation de sulfones allyliques substituées en position 1 - 106
IV. Conclusion - 116
Chapitre V : Additions radicalaires sur des époxydes vinyliques - 119
I. Quelques généralités sur les organoboranes - 121
II. Les trialkylboranes : des générateurs et des accepteurs de radicaux - 123
III. Premiers essais au laboratoire - 141
IV. Conclusion - 152
Chapitre VI : Les alcools allyliques comme agents allylants radicalaires - 155
I. β-élimination de radicaux oxygénés - 157
II. Les alcools allyliques comme agents dallylation radicalaire - 162
III. Additions radicalaires sur les oléfines préparées - 172
IV. Conclusion - 179
Chapitre VII : Synthèse de 5-arylpipéridin-2-ones par voie radicalaire - 183
I. Synthèse de pipéridin-2-ones substituées en position 5 - 185
II. Synthèse de 5-arylpipéridin-2-ones par voie radicalaire - 199
III. Conclusion - 216
Conclusion générale - 219
Partie expérimentale - 223
Chapitre IV : Allylations radicalaires basées sur des allyles sulfones substituées - 238
Chapitre V : Additions radicalaires sur des époxydes vinyliques - 264
Chapitre VI : Les alcools allyliques comme agents allylants radicalaires - 278
Chapitre VII : Synthèse de 5-arylpipéridin-2-ones par voie radicalaire - 320
Annexe 1 - 363
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