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Nouvelles réactions d'allylation radicalaire.

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.
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Nicolas Charrier. Nouvelles réactions d'allylation radicalaire.. Chimie. Ecole Polytechnique X, 2008. Français. ⟨pastel-00004272⟩

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