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Synthesis 2010(24): 4177-4187  
DOI: 10.1055/s-0030-1258286
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Towards a Flexible Strategy for the Synthesis of Enantiomerically Pure [2.2]Paracyclophane Derivatives: The Chemistry of 4-Tolylsulfinyl[2.2]paracyclophane

Rakesh Parmara, Martyn P. Colesa, Peter B. Hitchcocka, Gareth J. Rowlands*a,b
a Chemistry Division, Department of Chemistry and Biochemistry, University of Sussex, Falmer, BN1 9QJ, UK
b Institute of Fundamental Sciences - Chemistry, Massey University, Private Bag 11 222, Palmerston North, New Zealand
Fax: +64(6)3505682; e-Mail: g.j.rowlands@massey.ac.nz;
Further Information

Publication History

Received 6 August 2010
Publication Date:
05 October 2010 (online)

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Abstract

The use of enantiomerically enriched 4-tolylsulfinyl[2.2]paracyclophane as a precursor to a variety of mono- and di­substituted [2.2]paracyclophane derivatives is described. The goal of our research is to develop a single general precursor that permits the synthesis of the most common [2.2]paracyclophane substitution patterns. The chemistry of two diastereoisomers of 4-tolylsulfinyl[2.2]paracyclophane has been explored and it facilitates the synthesis of enantiomerically enriched 4-substituted and 4,13-disubstituted [2.2]paracyclophanes. Directed lithiations result in an unusual cyclisation reaction. Whilst the tolyl group cannot realise our goal, the chemistry outlined acts as a successful ‘proof of concept­.’

Key words

asymmetric synthesis - cyclophanes - sulfoxides - enantiomeric resolution

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7

This argument was originally stated in reference 5. Chemists that have worked with [2.2]paracyclophane might argue that the greatest impediment to advancing this field is the mercurial nature of these molecules that can hinder even the most simple-looking syntheses.

33

The crystal appears to contain the tribromo product co-crystallised with the dibromo product in a 2:1 ratio. There are two independent molecules with different conforma­-tions. In both the occupancy of the Br(3) atom is 0.67.