Novel synthetic approach for optical resolution of cryptophanol-A: a direct access to chiral cryptophanes and their chiroptical properties.
The separation by crystallization of the pair of cryptophane diastereomers 1 a and 1 b, obtained in 1:1 ratio by treating racemic anti cryptophanol-A (2) with (-)-camphanic acid chloride, provided a substantial amount of optically pure material (diastereomeric excess>98 %). Subsequent hydrolysis afforded the optically pure cryptophanol-A enantiomers (+)-2 and (-)-2, which were submitted to nucleophilic substitution reactions to provide cryptophane-A (+)-3 and cryptophane monoester (-)-4 in optically pure form. The chiroptical properties of the new cryptophanes 1-4 were investigated by using circular dichroism spectroscopy, and the absolute configuration of the molecules was clearly established. These new cryptophanes represent additional interesting examples for studying the Cotton effect of interacting multichromophoric systems. Moreover, this novel approach presents numerous advantages over the other methods developed so far to obtain optically pure cryptophanes, and compounds (-)-2, (+)-2, and (-)-4 can give access to new enantiopure functionalized cryptophanes with host-guest properties similar to those of cryptophane-A.
Brotin
Thierry
T
Ecole Normale Supérieure de Lyon, Stéréochimie et Interactions Moléculaires, UMR 5532 CNRS/ENS-Lyon, 46 Allée d'Italie, 69364 Lyon 07, France. tbrotin@ens-lyon.fr
Barbe
Romain
R
Darzac
Magali
M
Dutasta
Jean-Pierre
JP