4H-Pyran-4-thiones react with thallium(III) trifluoroacetate to form thallium-containing pyrylium trifluoroacetates which are ring-opened by water; the resulting intermediates spontaneously lose thallium(I) trifluoroacetate, with concomitant sulphur–oxygen bond formation, to give 1,6-dioxa-6a-thiapentalenes.
D. H. Reid and R. G. Webster, J. Chem. Soc., Chem. Commun., 1972, 1283 DOI: 10.1039/C39720001283
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