Synthesis 2008(23): 3769-3774  
DOI: 10.1055/s-0028-1083232
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Octahydro[1,4:5,8]dimethanoanthraquinone as a Cheap and Readily Avail­able Electron-Transfer Oxidant for Biaryl Synthesis from Organocuprates

Ruchi Shukla, Rajendra Rathore*
Department of Chemistry, Marquette University, P.O. Box 1881, Milwaukee, WI 53201, USA
Fax: +1(414)2887066; e-Mail: [email protected] ;
Further Information

Publication History

Received 18 July 2008
Publication Date:
14 November 2008 (online)

Abstract

The preparation of biaryls via oxidation of organocuprates with easily synthesized octahydro[1,4:5,8]dimethano­anthraquinone (DAQ) is described. The oxidative coupling of organocuprates using DAQ was successfully employed for the preparation of highly hindered biaryls and 9- and 10-membered macrocycles containing biaryl linkages. The oxidative reactivity of DAQ towards organocuprates is found to be similar to the commonly utilized quinones such as duroquinone (DQ) and tetra-tert-butylbiphenoquinone (BQ) and is in accord with their similar reduction potentials (measured by an electrochemical method). The structures of the quinones are also established with the aid of X-ray crystallography. The usage of DAQ for biaryl synthesis is advocated owing to the ready separation of reduced DAQ-H2 from biaryls as well as its ready-availability in multi-gram quantities.

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19

The low-precision crystal structures of DQ and BQ at r.t. are known, see CCDC database.

22

Crystallographic data (excluding structure factors) for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication numbers CCDC-701965, 701966, and 701967. Copies of the data can be obtained free of charge on appli-cation to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [E-mail: [email protected]; Fax: +44(1223)336033 or via www.ccdc.cam.ac.uk/conts/retrieving.html].