Marie-Paule Jouannetaud

Carbonic Anhydrases inhibitory effects of new benzenesulfonamides synthesized by using superacid chemistry

A series of benzofused sultams and fluorinated benzenesulfonamides were synthesized in superacid HF/SbF5 from simple N-allylic derivatives. Almost all of these original compounds showed micromolar inhibitory activities against carbonic anhydrases I and II. The fluorinated derivatives inhibit better the tumor-associated isoforms IX and XII, and one of the tested compounds showed inhibition in the nanomolar range.

Superelectrophilic activation in superacid HF/SbF(5) and synthesis of benzofused sultams.

The synthesis of benzofused sultams and/or fluorinated sulfonamides, starting from N-allylic sulfonamides, was performed in superacid HF/SbF(5), through superelectrophilic activation. A dramatic effect of superacid composition on the selectivity of the reaction was shown and applied to the synthesis of cyclic 4-aminobenzenesulfonamides.

A novel, facile route to beta-fluoroamines by hydrofluorination using superacid HF-SbF(5).

A range of unsaturated amines and sulfonamides were converted to beta-fluoro nitrogen analogues after hydrofluorination in superacid HF-SbF(5), based on the formation of highly reactive electrophilic intermediates.

Gem-difluorination of aminoalkynes via highly reactive dicationic species in superacid HF-SbF5: application to the efficient synthesis of difluorinated cinchona alkaloid derivatives.

A variety of alkynylated amines, amides, and imides are reacted in the superacid system HF-SbF5 to give regioselectively new beta-gem-difluoroamines. The reaction, which is not observed in pure HF, is consistent with the formation of a dicationic intermediate (i.e., both vinylic and adjacent protonated N-ammonium cations). Application to the regioselective and efficient synthesis of difluorinated cinchona alkaloid derivatives is described.

Selective synthesis of gem-chlorofluorinated nitrogen-containing derivatives after superelectrophilic activation in superacid HF/SbF5.

The first direct selective synthesis of novel gem-chlorofluorinated nitrogen-containing building blocks in superacid is reported. The dramatic role of the chlorine atom on the reaction is shown by in situ NMR experiments and allows the involvement of a novel original superelectrophilic activation process in superacid HF/SbF(5) to be postulated.

Regioselective electrophilic trifluoromethylation of substituted anilines and derivatives in superacid

Abstract In a one pot procedure, treatment of chloro or methyl substituted acetanilides in HF/SbF 5 /CCl 4 followed by addition of HF/pyridine yields trifluoromethyl derivatives with high regioselectivity.

Functionalization of a non activated CH bond: Fluorination of vindoline at C-20 in superacids

Abstract Reaction of vindoline 1a with NBS, NCS, H 2 O 2 in HF-SbF 5 yields 7β substituted (Br, Cl or OH)-20-fluoro-6,7-dihydrovindolines. These results imply reaction of the electrophile (Br + , Cl + and OH + equivalent) on the β-face of C-6 C-7 double bond to give oniums ions, followed by a 1,3-hydride shift from C-20 to C-6, and fluorination of the resulting ion.

Anti-Markovnikov additions to N-allylic derivatives involving ammonium–carbenium superelectrophiles

Anti-Markovnikov additions to non-conjugated unsaturated amines in superacid are reported. In situ NMR studies, DFT calculations and labelled substrates reactions support the involvement of new ammonium-carbenium superelectrophiles in this original process.

STEREOSELECTIVE IONIC HYDROGENATION OF VINCA ALKALOIDS AND VINORELBINE IN SUPERACIDS: AN ACCESS TO 4'R-REDUCED ANALOGS

Abstract Stereoselective ionic hydrogenation of vinblastine, anhydrovinblastine and vinorelbine in HF SbF 5 by methylcyclopentane yields the corresponding 4′ R reduced analogs. Deuterium labelling shows that the reduction occurs at C-20′.

Rearrangement of quinine in superacid: an efficient access to a novel chiral heterocyclic system

In superacid, quinine rearranges to yield a novel oxazapolycyclic compound.