Sulfonyl iodides, including three previously unknown alkane derivatives, add readily and stereoselectively to acetylenes to form 1: 1 adducts in good to excellent yields. That the addition occurs in a trans manner was established by reducing the adducts to the cis-vinyl sulfones with zinc and acetic acid and by three-dimensional X-ray crystallography. The adducts represent convenient precursors to sulfonylacetylenes and, on treatment with cuprous phenylacetylide, yield the novel ene-yne sulfones. The acetylenic sulfones undergo a smooth thermally induced extrusion of sulfur dioxide in several cases.
In 1894, Henriques reported that bis(2‐hydroxy‐1‐naphthyl) sulfide was converted to an isomeric dibasic substance by treatment with alkaline ferricyanide and a subsequent reduction of the intermediate obtained. Hinsberg carried out a similar sequence of reactions with bis(2‐hydroxy 1 naphthyl) sulfone. The structures of the isomeric products of the two series were established by Smiles who recognized the occurrence of a novel intramolecular nucleophilic rearrangement.
This chapter surveys the reactions, which because of the extensive work of Smiles, have been called Smiles rearrangements. They may be characterized as intramolecular displacements at aromatic rings initiated by nucleophilic centers located two or three atoms distant from the functional group which is displaced.
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