Calixarene Phosphorylation: Cation Control of Reaction Pathways

Lindsay Byrne, J.M. Harrowfield, D.C.R. Hockless, B.J. Peachey, Brian Skelton, Allan White

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

The hydroxide ion catalysed phosphorylation of p-t-butylcalix[4]arene by diethyl chlorophosphate under heterogeneous conditions shows a marked sensitivity to the nature of the phase transfer catalyst used. Thus, substitution of tetraethylammonium bromide for the tetrabutylammonium bromide prescribed for the synthesis of the calixarene tetraphosphate leads to a major reaction product becoming a bis(phosphate) in which the calixarene binds as a unidentate ligand to one phosphorus and as a bidentate ligand to the other. An X-ray crystal structure analysis on this new compound shows the calixarene to adopt a somewhat distorted 'cone' conformation with an unusual orientation of one of the t-butyl substituents into the cone cavity. It also reveals that a significant diastereoselectivity must operate in the formation reaction. The only other reaction product detected in this system appears to be the calixarene tetraphosphate in a partial cone conformation.
Original languageEnglish
Pages (from-to)1673-1683
JournalAustralian Journal of Chemistry: an international journal for chemical science
Volume46
DOIs
Publication statusPublished - 1993

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