Oxidized phenoxathiin-based macrocycles, easily accessible thiacalix[4]arene derivatives, consist of a unique set of structural elements representing a key prerequisite for the unexpected reactivity described in this paper. As proposed, the internal strain, imposed by the presence of a heterocyclic moiety, together with a number of electron-withdrawing groups (SO2) opens the way to the cleavage of the macrocyclic skeleton through a cascade of three SNAr reactions triggered by the nucleophilic attack of an SH- anion. The whole transformation, which is unparalleled in classical calixarene chemistry, leads to unique linear sulfinic acid derivatives with a rearranged phenoxathiin moiety that can serve as building blocks for macrocyclic systems of a new type.

Department of Organic Chemistry University of Chemistry and Technology Prague Technicka 5 166 28 Prague 6 Czech Republic

Department of Solid State Chemistry UCTP 166 28 Prague 6 Czech Republic

Laboratory of NMR Spectroscopy UCTP 166 28 Prague 6 Czech Republic

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Enantiodiscrimination of Inherently Chiral Thiacalixarenes by Residual Dipolar Couplings

Reactivity of phenoxathiin-based thiacalixarenes towards C-nucleophiles