A cis-directing effect towards diols by an exocyclic P-NHR moiety in cyclotriphosphazenes

Cyclophosphazenes containing the P-NHR moiety in an exocyclic spiro ring, N3P3Cl4[NH(CH2)3O], (1), and N3P3Cl4[NH(CH2)3NMe], (2), were used to investigate a possible directing effect of the P-NHR moiety on the formation of products in the nucleophilic substitution reactions with diols such as tetraethyleneglycol, 1,3-propanediol and 2,2-dimethyl-1,3-propanediol. The 31P NMR spectra of the reaction mixtures showed that only one kind of ansa product is formed in each of these reactions. X-ray crystallographic studies of the ansa products [(4a), (5a), (6a) and (7a)] have provided definitive proof of the cis-directing effect of the P-NHR moiety in cyclotriphosphazenes. It is likely that hydrogen-bond interaction between the incoming nucleophile and the P-NHR moiety of the reactant accounts for the preference for products with the substituents cis to the NH group.

Reactions of diols with cyclophosphazenes containing a P-NHR moiety in an exocyclic spiro ring lead to ansa derivatives that are exclusively cis rather than trans to the NH group.Figure optionsDownload as PowerPoint slide