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.
Key words
quinones - one-electron transfer - organocuprates - biaryls - macrocycles
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