Preparation of heteromacrocycles bearing two tetra-coordinate phosphorus atoms and at least two ferrocene units

Alberto Tárraga,Pedro Molina,David Curiel,Paul Krapcho

doi:10.3998/ark.5550190.0003.510

Abstract

A synthetic procedure has been developed for the preparation of a new type of macrocycle in which the ferrocene unit is appended to an O-N-P-macrocycle or it is incorporated within the macrocyclic unit. The methodology is based on the Staudinger reaction of a bis-azide with the appropriate diphosphine.

Highlights

Recent years have witnessed a significant interest in a new generation of abiotic macrocycles and cryptans that contain an electrochemical response function, such as the ferrocene unit, either attached to, or as integral part of, the ligand framework
We recently reported a new approach to the preparation of a new type of macrocycles bearing a disubstituted ferrocene moiety[5] and a kind of P,N-heterodifunctional ferrocene-coordinating open chain ligands[6] that is based on the Staudinger imination[7] of trivalent phosphorus compounds with azides to produce an iminophosphorane function after nitrogen evolution
The synthesis of phosphorus-containing macrocycles possessing an intracyclic C-P-N grouping have been previously reported[8] we wish to report the preparation of macrocycles containing two tetra-coordinate phosphorus atoms bearing two iminophosphorane moieties [macrocyclic bis(iminophosphoranes)] as well as the ferrocene unit both appended to the macrocycle or incorporated within the macrocycle framework

Summary

Introduction

Recent years have witnessed a significant interest in a new generation of abiotic macrocycles and cryptans that contain an electrochemical response function, such as the ferrocene unit, either attached to, or as integral part of, the ligand framework. The methodology used is based on the reaction of the bis-azide 3 with diphosphines of general structure R2P-Y-PR2 some of which have been used by Majoral and coworkers for the preparation of phosphorus-containing cryptands.[9] Frequently, the synthesis of macrocycles with chemically diverse donating (or bonding) atoms requires multistep manipulations with concomitantly low yields or difficult separations.

Results

Conclusion