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Chiral HPLC Separation, Absolute Structural Elucidation, and Determination of Stereochemical Stability of trans ‐Bis[2‐(2‐pyridinyl)aminophenolato] Cyclotriphosphazene
Author(s) -
Kajiyama Kazumasa,
Setone Yuki,
Aoyagi Kouki,
Yuge Hidetaka
Publication year - 2016
Publication title -
chirality
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.43
H-Index - 77
eISSN - 1520-636X
pISSN - 0899-0042
DOI - 10.1002/chir.22612
Subject(s) - chemistry , racemization , diastereomer , triethylamine , absolute configuration , enantiomer , chirality (physics) , high performance liquid chromatography , epimer , toluene , chiral column chromatography , pyridine , crystal structure , stereochemistry , medicinal chemistry , organic chemistry , chromatography , chiral symmetry breaking , physics , quantum mechanics , nambu–jona lasinio model , quark
Chiral high‐performance liquid chromatography (HPLC) separation of trans ‐bis[2‐(2‐pyridyl)aminophenolato] dichlorocyclotriphosphazene 1 was achieved and the absolute configuration of (+)-1 was assigned to be S,S by single‐crystal X‐ray structural analysis. The optically pure 1,2‐diphenyl‐1,2‐ethanediolate derivatives (+)‐ 2a and (−)‐ 2b were synthesized by the reactions of (+)-1 and (-)-1 with ( R,R )‐hydrobenzoin, respectively, in refluxing toluene in the presence of an excess amount of triethylamine and a catalytic amount of 4‐(dimethylamino)pyridine. The racemization of the enantiomers of 1 and the epimerization of diastereomers of 2 were not observed in refluxing toluene neither under acidic nor basic conditions. The stereochemistry of (+)-1 was confirmed by the crystal structure of (+)‐ 2a and bis[(4‐methyl‐2‐pyridyl)oxy]cyclotriphosphazene (+)-3 derived from (+)-1 . Chirality 28:556–561, 2016 . © 2016 Wiley Periodicals, Inc.