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.
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