The Usefulness of Trivalent Phosphorus for the Synthesis of Dendrimers.

Anne-Marie Caminade,Béatrice Delavaux-Nicot,Kathleen I Moineau-Chane Ching

doi:10.3390/molecules26020269

Abstract

Dendrimers are hyperbranched macromolecules, which are synthesized step-by-step by the repetition of a series of reactions. While many different types of dendrimers are known, this review focusses on the use of trivalent phosphorus derivatives (essentially phosphines and phosphoramidites) for the synthesis of dendrimers. The first part presents dendrimers constituted of phosphines at each branching point. The other parts display the use of trivalent phosphorus derivatives during the synthesis of dendrimers. Different types of reactions have been applied to phosphines. The very first examples of phosphorus-containing dendrimers were obtained by the alkylation of phosphines. Then, several families of dendrimers were elaborated by reaction of phosphoramidites. Such a type of reaction is the base of the solid phase synthesis of oligonucleotides; it has been applied in particular for the synthesis of dendrimers constituted of oligonucleotides. Finally, the Staudinger reaction between phosphines and azides afforded different families of dendrimers, and was at the origin of accelerated methods of synthesis of dendrimers. Besides, the reactivity of the P=N-P=S linkages created by this reaction led to very original dendritic structures.

Highlights

Dendrimers are macromolecules constituted of regular branching layers, obtained by the step-by-step association of identical monomers
Such a type of reaction is the base of the solid phase synthesis of oligonucleotides; it has been applied in particular for the synthesis of dendrimers constituted of oligonucleotides
The most important methods of synthesis for this second type of dendrimers elaborated with the help of tricoordinated phosphorus derivatives are the alkylation of phosphines, the use of phosphoramidites followed by oxidation, and the Staudinger reaction of phosphines with azides [7]

Summary

Introduction

Dendrimers are macromolecules constituted of regular branching layers, obtained by the step-by-step association of identical monomers. Ods of synthesis for this second type of dendrimers elaborated with the help of tricoordinated phosphorus derivatives are the alkylation of phosphines, the use of phosphoramidites followed by oxidation, and the Staudinger reaction of phosphines with azides [7]. The most important methods of synthesis for this second type of dendrimers elaborated with the help of tricoordinated phosphorus derivatives are the alkylation of phosphines, the use of phosphoramidites followed by oxidation, and the Staudinger reaction of phosphines with azides [7]. The phosphine was used for the complexation of gold, affording 7-G2-Au (Scheme 7) [13] In another experiment, a MMoloelceuculelses2022012,12, 62,6x, xFFOORRPPEEEERRRREEVVIpEIEWhWosphorane was used as a very original quinque-directional core for the synthesis o8f8otofhf3e434 first generation phosphonium dendrimer (Figure 3) [13]. The P=N function created by this reaction is very sensitive to water, and is cleaved to generate a primary amine on one side

The Staudinger Reaction for the Synthesis of Regular Dendrimers

Conclusions