Synthesis of novel paracyclophanes with linear P,N-containing spacers

Condensation of bis(hydroxymethyl)mesityl-and bis(hydroxymethyl)phenylphosphines with N,N'-disubstituted bis(4-aminophenyl)methanes and bis(4-amino-3-carboxyphenyl)methane occurred as covalent self-assembly spontaneously giving a mixture of trans-and cis-diastereomers of 1,5,19,23-tetra-R'-3,21-di-R-1,5,19,23-tetraaza-3,21-diphospha[5.1.5.1]paracyclophanes as the major products. The trans-isomer (R is mesityl; R' is methyl) was isolated in the individual state and structurally characterized by X-ray diffraction analysis. Sulfurization of macrocyclic diphosphines (R = Ph; R' is 3-pyridylmethyl or 4-pyridylmethyl) gave the corresponding diphosphine disulfides, the trans-stereoisomer being isolated in the individual state.