6533b7dcfe1ef96bd1271b62

RESEARCH PRODUCT

Synthesis of ortho-fonctionnalized arylphosphines and their applications

subject

description

This thesis reports with the synthesis of ortho-functionnalized phosphines bearing phosphonium and 1,2,3-triazole moieties.The synthesis of phosphines-phosphoniums, using as key-step Phospha-Fries rearrangement and Appel reaction is described. Eight new phosphines- phosphoniums, bearing aryl, alkyl or ferrocenyl fragments on the phosphonium part, have been prepared with overall yields reaching 48%. These phosphines- phosphoniums have been used in the preparation of gold (I) complexes which have been characterized using spectroscopic methods and X ray diffraction. Both gold (I) complexes and phosphines-phosphoniums have been studied in biology and these compounds turned out to be cytotoxic in-vitro toward different cancerous cell lines with sub- micromolar IC50.The stereoselective synthesis of P-chirogenic phosphines-triazoles has been carried out using « ephedrine’s method » and « click chemistry ». Several methodologies, using P-chirogenic electrophilic synthons as methyl phosphinites borane (or not), chlorophosphines borane as well as borane and sulfur protecting group on phosphorus center have been described. The use of P-chirogenic thiophosphines-alkynes as key-compounds has allowed to obtain new P- chirogenic phosphines- triazoles with enantiomeric purity up to 99%. Palladium and iridium complexes have been prepared with P- chirogenic phosphines-triazoles and their coordination study have shown a P-N bidentate chelation mode. The phosphines- triazoles have been applied in asymmetric allylic alkylation and hydrogenation catalyzed by palladium and iridium complexes and allowed to obtain enantioselectivities up to 84%. Finally, P-chirogenic phosphines-alkynes have been also applied in asymmetric catalysis in allylic alkylation reaction in presence of palladium complexes to give enantiomeric excesses up to 67%.