Synthesis of Bis(BINOL) Substituted 2,2′-Bipyridines and their Late Transition Metal Complexes

Abstract

Bis(BINOL) substituted 2,2′-bipyridines (1a and 1b) have been prepared via a twofold Sonogashira cross-coupling reaction from 3-iodo-2,2′-di(methoxymethoxy)-1,1′-binaphthyl (4) and 5,5′-diethynyl-2,2′-bipyridine (2), which could be synthesised through a palladium mediated homodimerisation using zinc powder as a reducing agent. 1a and 1b form well defined silver(I), copper(I) or zinc(II) complexes [M1 ₂]⁺ and [Zn1a ₂]²⁺ thereby orienting the BINOL groups in a fashion potentially useful for molecular recognition of chiral substrates.

Key words

cross-coupling reactions - palladium - ligands - complexes - supramolecular chemistry

References

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Lützen, A.; Thiemann, F.; Meyer, S. Synthesis 2002, submitted for publication.

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Molecular modelling was performed using commercially available PC Spartan Pro software package from Wavefunction.

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The homodimerisation is usually finished after a few hours as indicated by thin-layer chromatography. However prolonged heating resulted in increased formation of by-products. Also change of the solvent from DMF to THF gave only a mixture of unreacted chloropyridine and 3.