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1,1′‐Bi(trishomobarrelenyl) – Synthesis and Chiroptic Properties
Author(s) -
de Meijere Armin,
Rauch Karsten,
Schrader Bernhard,
Brackmann Farina,
Pfoh Roland,
Rühl Stephan,
Katoh Yasunaka,
Okamoto Yoshio,
Wodrich Matthew D.,
Corminboeuf Clémence,
Schreiner Peter R.
Publication year - 2009
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.200801111
Subject(s) - chemistry , enantiomer , diastereomer , pentane , absolute configuration , yield (engineering) , amine gas treating , enantiomeric excess , stereochemistry , molar ratio , chiral column chromatography , chirality (physics) , crystallography , organic chemistry , enantioselective synthesis , catalysis , materials science , nambu–jona lasinio model , chiral symmetry breaking , physics , quantum mechanics , quark , metallurgy
Abstract 1,1′‐Bi( endo , exo , syn ‐pentacyclo[3.3.3.0 2,4 .0 6,8 .0 9,11 ]undecyl)[1,1′‐bi(trishomobarrelenyl)] ( 4 ) has been prepared as a 1:1 mixture of its meso ‐ and d , l ‐diastereomers in six steps from trishomobarrelene 1 via the amine 5 , the N , N ′‐bis(trishomobarrelenyl)sulfamide 6 and the 1,2‐(trishomobarrelenyl)diazene 7 in 16 % overall yield. Crystals of meso ‐ 4 were grown from a pentane solution of the mixture and subjected to an X‐ray structure analysis. The (+)‐ and the (–)‐enantiomer were isolated by HPLC on a chiral‐phase column. They exhibited significantly enhanced molar optical rotations which are consistent with the presence of three helically arranged 1,2‐dicyclopropylethane units in their skeletons. The absolute configuration of the (+)‐enantiomer was assigned on the basis of DFT computed optical rotations of both enantiomers to be all ‐( S ).(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)