Synthèse et Réactivité d'Allènes par Transferts d'Hydrures Catalysés à l'Or (I).

Abstract : This PhD thesis deals with the development of new gold(I)-catalyzed reactions involving a hydrogen atom as a formal hydride, and as an intramolecular nucleophile to promote a C-H functionalization and the formation of new carbon-carbon bonds. The Chapter 1 and 2 describe the recent developments in the homogeneous gold catalysis and the C-H bond functionalization strategies, particularly those in which a 1,5-hydride shift takes part. The Chapter 3 gives details of the synthesis of polysubstituted allenes. This new method is based on the activation of a propargyl benzyl ether by a gold(I) complex which promotes a 1,5-hydride shift/fragmentation sequence and produces a molecule of allene. This represents a new access route to very popular skeletons in organic synthesis. Allene hydrofunctionalization reactions using a hydride transfer strategy are then developed in the chapter 4. These new reactions take advantage of the electrophilic activation of allenes by a gold(I) complex or a Brønsted acid catalyst to lead to a 1,5 hydride shift/cyclisation sequence. They enable the preparation of variously substituted oxygenated heterocycles of great pharmaceutical interest. Finally, the chapter 5 presents a combination of the two previous methodologies. This new synthetic approach allows gold(I)-catalyzed hydride shifts cascades. A larger diversely substituted spirotetrahydrofurans, tetrahydropyrans and oxepanes line could thus be obtained in a diastereoselective manner.
Document type :
Theses
Organic chemistry. Ecole Polytechnique X, 2012. French


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Submitted on : Monday, February 11, 2013 - 4:59:48 PM
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Benoît Bolte. Synthèse et Réactivité d'Allènes par Transferts d'Hydrures Catalysés à l'Or (I).. Organic chemistry. Ecole Polytechnique X, 2012. French. <pastel-00787282>

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