Cyclophosphorylation of Polyphenols by Diamidoarylphosphites.

Abstract

Phosphorylation Phosphorylation O 0278Cyclophosphorylation of Polyphenols by Diamidoarylphosphites. -The phosphorylation of polyphenols with aromatic diamidophosphites proceeds by an anomalous pathway via rupture of only one P-N bond and one P-O bond, whereas the second P-N bond remains intact. In the reaction of bisphenols (VII) with phosphite (VIII) [and also with (II)], intermediates like (IX) are isolated which under higher reaction temperatures undergo cyclization to give dioxaphosphocines (X). It is supposed that the unusual lack of reactivity of the second P-N bond is due to the spatial arrangement of this amido group with respect to the reaction site in phosphorylated intermediates such as (IX). -(MASLENNIKOVA, V. I.; MERKULOV, R. V.; DYAGILEVA, M. V.; VASYANINA, L. K.; LYSSENKO, K. A.; ANTIPIN, M. Y.; WEBER, D.; BAUER, I.; HABICHER, W. D.; NIFANTYEV*, E. E.; Tetrahedron 59 (2003) 10,

Phosphorus-containing macrocyclic compounds: synthesis and properties

“…139 The regioselectivity of the reaction was analyzed by studying the reaction of octols 93a,d,g, whose molecules contain different substituents in the cyclophane core, with hexaethylphosphoric triamide.…”

“…In this case, lyophilic interactions between long hydrocarbon chains would be expected to exist, resulting in the predominant formation of the cone conformation, which, in turn, will facilitate the cyclophosphorylation. 139 Polyfunctional cavitands 188 were synthesized by the reaction of hexaalkylphosphoric triamides with aminoalkylated derivatives of calix [4]resorcinols 189 (Scheme 63). 141 ± 144 The effect of dialkylaminomethyl groups is manifested in that cavitands 188, unlike their unsubstituted analogues, are easily hydrolyzed in air.…”