Abstract: The chlorination of thiane 1-oxides containing large substituents gave a-chloro sulfoxides with the chlorine atom in the axial and the oxygen atom in the equatorial position, independent of the configuration at the sulfur of the starting material. Thiane 1-oxides containing small substituents do not undergo a sulfur but, rather, a ring inversion to place the oxygen in the equatorial position before being halogenated axially at the a positions. ...
