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Synthesis 2002(5): 0655-0663
DOI: 10.1055/s-2002-23541
PAPER
© Georg Thieme Verlag Stuttgart · New York

The First Efficient Synthesis and Optical Resolution of Monosubstituted Cyclotribenzylenes

Carsten Schmuck*, Wolfgang Wienand
Institut für Organische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg, Germany+49(931)8884606
e-Mail: schmuck@chemie.uni-wuerzburg.de;
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Publication History

Received 24 January 2002
Publication Date:
02 April 2002 (online)

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Abstract

A new and high yielding synthetic route to monosubstituted cyclotribenzylenes 6 via the cyclocondensation of benzene with a suitably monosubstituted diol 20, obtained from ozonolysis of the corresponding dibenzosuberene precursor 19, was developed for the first time! The dibenzosuberene itself could be readily prepared in large quantities from inexpensive starting materials in five steps. Using this synthetic approach, a mono bromosubstituted cyclotribenzylene 12a was synthesized on large scale. Another four monosubstituted cyclotribenzylenes 21-24 were also prepared either via bromine/lithium exchange followed by subsequent quenching with external electrophiles or a copper mediated reaction with cyanide. These molecules adopt a rigid crown conformation as shown by X-ray analysis and temperature dependent NMR studies. The barrier to inversion is quite high, requiring temperatures well above 120 °C before inversion takes place. Futhermore, such monosubstituted cyclotribenzylenes are planar chiral and after optical resolution, using HPLC, we were able to obtain the first planar chiral C1-symmetric cyclotribenzylenes in form of the optically pure enantiomers of 12a, the CD spectra of which are exact mirror images over the entire spectral range.

Key words

carbocycles - cyclophanes - CD spectroscopy - planar chirality

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1

Former address: Institut für Organische Chemie, Universität zu Köln, Greinstrasse 4, 50939 Köln, Germany.

24

LiAlH4 even in equimolar amounts at low temperatures caused substantial debromination and gave only 23%, at most, of the desired bromosubstituted diol 20. Other reducing agents such as sodium boronate or lithium boronate only gave complex product mixtures in which the desired diol 20 was only present in small amounts (according to TLC and GC-MS analysis), no matter which reaction conditions we tried (e.g. by variation of temperature and solvent, respectively). Borane in THF did not react at all.