C-3-Symmetric Tricyclo[2.2.1.0(2,6)]heptane-3,5,7-triol

A straightforward access to a hitherto unknown C-3-symmetric tricyclic triol both in racemic and enantiopure forms has been developed. Treatment of 7-tert-butoxynorbornadiene with peroxycarboxylic acids provided mixtures of C-1- and C-3-symmetric 3,5,7-triacyloxynortricyclenes via transannular -cycl...

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Bibliographic Details
Published inAngewandte Chemie International Edition Vol. 56; no. 48; pp. 15456 - 15460
Main Authors Kozel, Volodymyr, Daniliuc, Constantin-Gabriel, Kirsch, Peer, Haufe, Guenter
Format Journal Article
LanguageEnglish
Published WEINHEIM Wiley 27.11.2017
Subjects
Chemistry
Chemistry, Multidisciplinary
Physical Sciences
Science & Technology
neighboring-group effects
ASYMMETRIC CATALYSIS
ENANTIOSELECTIVE ALLYLIC OXIDATION
MICHAEL ADDITION
CINCHONINE-SQUARAMIDE
nortricyclene
LIGANDS
chiral resolution
LIQUID-CRYSTALS
C-3 symmetry
CHIRAL MOLECULAR RECOGNITION
BORANE REDUCTION
RECEPTORS
transannular cyclization
C3 symmetry
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Summary:A straightforward access to a hitherto unknown C-3-symmetric tricyclic triol both in racemic and enantiopure forms has been developed. Treatment of 7-tert-butoxynorbornadiene with peroxycarboxylic acids provided mixtures of C-1- and C-3-symmetric 3,5,7-triacyloxynortricyclenes via transannular -cyclization and replacement of the tert-butoxy group. By refluxing in formic acid, the C-1-symmetric esters were converted to the C-3-symmetric formate. Hydrolysis gave diastereoisomeric triols, which were separated by recrystallization. Enantiomer resolution via diastereoisomeric tri(O-methylmandelates) delivered the target triols on a gram scale. The pure enantiomers are useful as core units of dopants for liquid crystals.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201709279