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A Synthetic Approach to Macrocyclic, Chiral Phosphane Derivatives with Crown‐Ether‐Like Structures
Author(s) -
Theil Agnès,
Hitce Julien,
Retailleau Pascal,
Marinetti Angela
Publication year - 2006
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200500455
Subject(s) - chemistry , moiety , crown ether , enantioselective synthesis , ether , catalysis , ring (chemistry) , oxide , medicinal chemistry , organic chemistry , polymer chemistry , stereochemistry , ion
( 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 1 H NMR analysis. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)