Jérôme Thibonnet

Domino allylic amination/Sonogashira/heterocyclisation reactions: palladium-catalysed three-component synthesis of pyrroles

Three-component reactions with 3,4-diiodoalk-2-enoic derivatives, primary amines, and terminal alkynes proceeded to give trisubstituted pyrroles in fair to good yields in the presence of palladium and copper catalysts under mild reaction conditions.

SYNTHESIS OF ETHYL (13E)-TRIFLUOROMETHYLRETINOATE AND ITS ANALOGUES BY PALLADIUM-CATALYSED CROSS-COUPLING

Abstract Stereoselective construction of ethyl (13 E )-trifluoromethylretinoate was achieved through two successive Stille reactions. The coupling of ( E )-1,2-bis(tributylstannyl)ethene and ethyl ( Z )-4,4,4-trifluoro-3-iodobut-2-enoate was performed first and followed by iododestannylation. The second step involved another vinyltin which was synthetised by stannylmetallation of the Nigishi dienyne 4c derived from β-ionone. Certain yne analogues were also prepared through Sonogashira coupling with 4c,d and ethyl 5-iodo-3-trifluoromethyl-pent-2,4-dienoate 3 .

Regioselective Copper-Mediated Synthesis of Thieno[2,3-c]pyrane-7-one, Indolo[2,3-c]pyrane-1-one, and Indolo[3,2-c]pyrane-1-one

In the presence of copper(I) iodide, heteroaromatic β-iodo-α,β-unsaturated carboxylic acid systems opposed to terminal alkyne afford selectively 6-endo-dig cyclization products via a tandem coupling oxacyclization reaction.

Carboxylate‐Directed Tandem Functionalisations of α,β‐Dihaloalkenoic Acids with 1‐Alkynes: A Straightforward Access to (Z)‐Configured, α,β‐Substituted γ‐Alkylidenebutenolides

An easy and mild copper(I)-catalysed lactonisation of readily available (E)-2,3-dihalopropenoic acid derivatives regio- and stereoselectively leads to rarely described (Z)-3-halo-5-ylidene-5H-furan-2-ones. These compounds are subsequently able to undergo classical Pd-catalysed cross-coupling reactions, providing 3-substituted and 3,4-disubstituted 5-ylidene-5H-furan-2-ones

Stereoselective access to functionalized β-γ unsaturated acids

Stereoselective synthesis of vinylstannanes bearing a carboxylic acid function was achieved from β-γ alkynoic acids via hydrostannation, stannylcupration or silastannation reactions. Regioselectivity is highly dependent on the nature of the stannylanions used and on protection of the carboxylic acid function.

TRIBUTYLSTANNYL 4-TRIBUTYLSTANNYLBUT-3-ENOATE : A USEFUL C-4 HOMOLOGATING AGENT. APPLICATION TO THE SYNTHESIS OF ARYL IODOLACTONES

Abstract Tributylstannyl 4-tributylstannylbut-3-enoate, readily prepared by radical hydrostannation, is used for the transfer of a but-3-enoic acid synthon. Some of the potentialities of this synthon are established by the synthesis of aryl iodolactones or tetralones (one of them is a key intermediate for ABT-200 synthesis).

Dramatic influence of the substitution of alkylidene-5H-furan-2-ones in Diels–Alder cycloadditions with o-quinonedimethide as diene partner: en route to the CDEF polycyclic ring system of lactonamycin

An efficient and rapid synthesis of the CDEF ring system of lactonamycinone is reported via a highly chemo- and diastereoselective intermolecular Diels-Alder cycloaddition between trans-1,2-disilyloxybenzocyclobutene and the appropriate γ-alkylidenebutenolide. The feasibility and the total chemoselectivity of the [4 + 2] cycloaddition for the construction of a spirolactone moiety via an intramolecular approach (IMDA) using both partners is also described demonstrating the versatility of the γ-alkylidenebutenolide building block.

Cross-coupling reaction: stereoselective synthesis of (E)-aryl or heteroarylvinylgermanes

Abstract ( E )-Aryl or heteroarylvinylgermanes are obtained by Stille reactions using ( E )-1-tributylstannyl-2-trialkyl (or triphenyl) germylethylenes.

Recent advances in development of materials for laser target

Nearly ten years ago, a research program concerning materials and technologies was defined to develop the very complex cryogenic target for obtaining the combustion of a deuterium-tritium mixture by inertial confinement fusion in the laser megajoule facility. The CEA target fabrication project includes research and development on various organic polymers and materials for the cryogenic laser megajoule target assembly as well as for other targets that can be useful for the fusion program (pre and post-ignition). Recent advances have been accomplished concerning the development of specific organic materials for the fabrication of targets components, including the synthesis of polymers for the laser megajoule microshells and metal-doped organic foams for the elaboration of doped-foam microshells or for the micromachining of components.

Stereospecific synthesis of functional alkenylsilanes via silastannation of but-3-ynoic acid

Tributylstannyl-(Z)-3-tributylstannyl-4-trimethylsilylbut-3-enoate is prepared by the stereospecific addition of (tributylstannyl)-trimethylsilane on the but-3-ynoic acid. Some of the potentialities of this synthon are established through cross-coupling and reverse cross-coupling reactions.