A Synthetic Approach to Macrocyclic, Chiral Phosphane Derivatives with Crown‐Ether‐Like Structures

Abstract

Abstract(S,S)‐Bis(2‐hydroxypropyl)(phenyl)phosphane oxide has been prepared, either by ring‐opening of (S)‐propylene oxide with dilithio(phenyl)phosphane or by catalytic hydrogenation of bis(2‐oxopropyl)(phenyl)phosphane oxide, promoted by ruthenium/MeO‐BIPHEP. Catalytic hydrogenation also allowed the enantioselective synthesis of (R,R)‐bis(2‐phenyl‐2‐hydroxyethyl)(phenyl)phosphane oxide from the corresponding diketone. These bis(β‐hydroxyalkyl)phosphane derivatives are suitable chiral starting materials for the synthesis of 1‐phospha‐10‐aza‐18‐crown‐6 derivatives, the first examples of optically pure, crown‐ether‐like, phosphorus‐containing macrocycles. One of them has been characterised by X‐ray diffraction study. Complexation of Na+ by the crown ether moiety of the macrocyclic ring has been observed by 1H NMR analysis. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)