6533b85bfe1ef96bd12bbcb7

RESEARCH PRODUCT

Synthèse de mono et diphosphines dérivées d'amino acides ou de peptides, appliquées en chimie de coordination et pour le greffage de fullerène C60

subject

description

The synthesis of secondary phosphine borane amino acids or dipeptides and their applications for the preparation of chiral ligands or for the grafting of fullerene, is described. These compounds were synthesized in good yield (up to 98%) without racemization. The principle of the synthesis is based on the alkylation of primary phosphine borane with a γ-iodo amino acid using phase transfer conditions. Tertiary diphosphine amino acids are obtained with 70% yield after a second alkylation. These compounds are one of the first examples of diphosphine grafted with a P-C bond on the side chain of amino acid. First of all, mono and diphosphine amino acid derivatives were used in asymmetric allylic substitution with palladium precursor or in asymmetric hydrogenation with rhodium precursor. In another hand, a cis platinum complex was synthesized with 60% yield from the diphosphine amino acid derivative. The cytotoxic properties of this complex were tested against human ovarian carcinogenic cell lines A2780. In the second part, the secondary phosphine borane amino acids and peptides have been used for grafting fullerene C60 by hydrophosphination using phase transfer conditions. The electrochemical study of the fullerene amino benzyl ester derivative has shown the cleavage of the P-C60 bond by electrolysis, affording the free fullerene and the secondary phosphine borane amino ester moiety. This work opens new perspectives for the chemistry of fullerene and phosphine derivatives of amino acids and peptides.