Jean-Pierre Pulicani

PREPARATION OF 7-MODIFIED DOCETAXEL ANALOGS USING ELECTROCHEMISTRY

The electrochemical reduction of 7α-iodo docetaxel at E-1.3V vs. SCE in methanol in the presence of lithium chloride and hydrochloric acid leads predominantly to 7-deoxy-docetaxel 9. When the electroreduction is conducted at E-1.7V vs. SCE in the presence of sodium acetate and acetic acid, the cyclopropanol-containing taxoid 10 is formed in good yield. Electrochemical reduction of 7-deoxy-docetaxel at C-10 is also reported. All these docetaxel analogs retain biological activity.

Direct access to 2-debenzoyl taxoids by electrochemistry, synthesis of 2-modified docetaxel analogs

Abstract A new route to semisynthetic 2-modified docetaxel analogs is described using electrochemical cleavage of the 2-benzoate as the key reaction. Subsequent reacylation at C-2 followed by sequential deprotections afforded the title analogs. Biological results of selected 2-docetaxel analogs are presented.

Electrochemical reduction of taxoids: Selective preparation of 9-dihydro-, 10-deoxy- and 10-deacetoxy-taxoids

The electrochemical reduction of docetaxel in methanol in the presence of ammonium chloride leads to 9α-dihydro-docetaxel 3 and 9β-dihydro-docetaxel 4. Under the same conditions, the electrochemical reduction of paclitaxel gives 10-deacetoxy-paclitaxel 7. Calcium chloride as well as magnesium and cerium chloride, and to some extent strontium and lithium chloride, favor 10-dehydroxylation in the docetaxel series. All these docetaxel analogs retain biological activity.

Improved access to 19-nor-7β, 8β-methylene-taxoids and formation of a 7-membered C-ring analog of doxetaxel by electrochemistry

Abstract A new route to semisynthetic 19-nor-7β, 8β-methylene taxoids, such as compound 8 , from the 7-O-trifluoromethanesulfonyl derivative 6 is reported. Evidence for a dissociation of the triflate to form a carbocation at C-7 under the reaction conditions is presented. Electrochemical reduction of the cyclopropane taxoid 8 gives, besides the expected 10-dehydroxy-cyclopropane analog 10 , the 7-membered C-ring derivative 11 .

Reduction electrochimique de la fonction amide d'un compose antitumoral, l'echinosporine

Abstract The electrochemical reduction of the amide group of echinosporine on mercury leads to the corresponding alcohol or aldehyde according to the operative conditions, with no hydrolysis of the lactone function.