Design and Study of PhosphocavitandsA New Family of Cavity Systems

Abstract

The design of phosphorus-containing cavity architectures that are of interest for biomimetics and other interdisciplinary sciences is among the most high-priority lines of research in modern organophosphorus chemistry. This Account acquaints the readers with methods for the design of rigid phosphomacrocyclic systems based on resorcinarenes, which differ in the nature of the phosphorus functions on the upper rim of the molecular bowl and have fixed dimensions of the molecular cavity. The authors demonstrate the possibility of attaining stereoselectivity in the synthesis of phospho(III)cavitands and their various transformations.

Synthesis of (PIII, PIII)-, (PIII, PV)-, (PIII, PIV)-, (PIV, PV)-, and (PV, PV)-Diphosphorus-Containing Compounds Based on 1,2,3- and 1,2,4-Trihydroxybenzenes

“…3 There are no systematic data concerning of the phosphorylation of polyhydroxyarenes using phosphorus halides. Here the data on phosphorylation of compounds (1, 2) by phosphorus trichloride are presented and the reactivity of the obtained diphosphorus-containing products relative to 3,6-di(tert-butyl)-1,2-benzoquinone, phosphorus pentachloride, and sulfuryl chloride is demonstrated.…”

Polymerization with Ditopic Cavitand Monomers

“…The key player of the whole class is the tetraphosphonate cavitand Tiiii [25], presenting all four P¼O bridging groups oriented inward with respect to the cavity (Figure 4.4). The stereospecific synthesis of this isomer requires bridging a suitable resorcinarenes with four P(III) units and then oxidizing them in situ with hydrogen peroxide [31]. Its peculiar complexation ability is the result of three interaction modes, which can be activated either individually or in combination by the host according to the guest requirements: (i) multiple ion-dipole interactions between the inward facing P¼O groups and the positively charged guests [32], (ii) single or multiple H-bonding involving the P¼O groups [33], and (iii) CH 3 -p interactions between an acidic methyl group present on the guest and the p-basic cavity of the host [34].…”

Regioselective Synthesis and Structure of New OligophosphorylatedrcttResorcinarenes

“…1,10-13 The use of reagents containing several active bonds enables the development of a competitive phosphocyclization process, resulting in the formation of phosphocavitands C ( Figure 1). 10,[14][15][16] This regiodirection of phosphorylation is contributed by the spatial proximity of hydroxyl groups, which is typical of the resorcinarenes with the rccc configuration of the R groups and existing in the crown conformation. 17 The maximum spatial separation of hydroxyl groups is characteristic of resorcinarenes with the rctt configuration of the R groups and existing in the chair conformation.…”