Arylation of thiacalix[4]arenes using organomercurial intermediates

Abstract

Direct mercuration of thiacalix[4]arenes immobilized in the cone or 1,3-alternate conformations followed by Pd-catalyzed arylation was applied to achieve either meta- or para-substitution of basic skeletons. The arylated products represent unique substitution patterns in thiacalixarene chemistry and their conformational behaviour was studied using a combination of dynamic NMR techniques and X-ray crystallography. The usefulness of organomercurial intermediates was also demonstrated through the preparation of thiacalix[4]arene dimers so far unknown in thiacalixarene chemistry.