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Synthesis 2008(16): 2551-2560  
DOI: 10.1055/s-2008-1067184
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Convergent Synthesis of 1,1′-Biisoquinolines Tethered to Calamitic Subunits

Elisabeth Kapatsina, Marie Lordon, Angelika Baro, Sabine Laschat*
Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany
e-Mail: sabine.laschat@oc.uni-stuttgart.de;
Further Information

Publication History

Received 22 April 2008
Publication Date:
17 July 2008 (online)

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Abstract

A convergent synthesis of a series of 4,4′-functionalized 1,1′-biisoquinolines via 1-chloro-4-hydroxyisoquinoline and substituted biphenyl- and phenylpyrimidine ethers as building blocks is described. The latter were prepared by Williamson etherification of the respective 4-hydroxybiphenyl and -phenylpyrimidine precursors with dibromoalkanes, allowing variation of the spacer lengths. 1-Chloro-4-hydroxyisoquinoline was obtained from N-phthalimidoglycine ethyl ester through a Gabriel-Colman reaction as a key step. Linkage of the building blocks by etherification in the presence of potassium carbonate gave the isoquinolines, which were submitted to a nickel(II) chloride mediated homocoupling to yield the ligand systems.

Key words

biisoquinolines - biphenyls - ligands - homocoupling - Williamson etherification

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16

Application of the catalyst system NiCl2˙6H2O/Zn/PPh3 to
4-ethoxy-1-bromoisoquinoline yielded only 38% of the desired 1,1′-biisoquinoline 22a, whereas no product was formed with NiBr2(PPh3)2/Zn/Et4NI. As the latter system catalyzed the reaction with 4-ethoxy-1-chloroisoquinoline, the experiments were carried out with chloroisoquinolines 20 in the presence of nickel chloride as the catalyst.