Stereogenic properties of spiranes combined with four equivalent conventional centres of chirality

Abstract

Derivatives of the tri-spirane pentaerythritoxy-cyclophosphazene compound, 1, have been used to investigate the stereogenic properties of spiranes combined with four equivalent conventional centres of chirality. In compound 1 the two inner rings are carbocyclic and symmetrical and the two outer rings are cyclotriphosphazenes substituted in different positions to provide the conventional centres of chirality. The case of combining spiranes with four equivalent centres of chirality has been investigated by the reaction of 1 with dimethylamine in a 1 : 8 molar ratio to give four diastereoisomeric products, in which the two cyclophosphazene rings are non-geminally di-substituted in either cis or trans configurations; viz. the cis–cis (2a), cis–trans (2b) and two trans–trans substituted dimethylamine derivatives 2c and 2d. The structure and stereogenic properties of compound 2a (C₂ symmetry) have been characterized previously by both X-ray crystallography and ³¹P NMR spectroscopy on addition of a chiral solvating agent (CSA) and the structures and stereogenic properties of compounds 2b (C₁) and 2d (C₂) have been similarly characterized in this work. The structure of compound 2c has been characterised by X-ray crystallography and found to be meso with the relatively rare S₄ symmetry. The four diastereoisomeric products 2a–2d represent all the possible stereochemical isomers of a spirane combined with four equivalent conventional centres of chirality.