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The structures of two new T-shaped selenyl chloride adducts studied by experimental (multinuclear NMR, IR, and Raman spectroscopy and X-ray diffraction analysis) and theoretical (ab initio and DFT quantum chemical calculations) methods clearly demonstrate the possibility of propeller-like free rotation of the SeCl2 moiety around the C–Se bond and indicate the absence of any significant double-bond character.

The novel fused selenazole heterocycles (V) and (VII) are formed both diastereo- and regioselectively.

In recent years, we have developed a new approach to the synthesis of sulfur and nitrogen containing hetero cycles based on the polar cycloaddition of hetarenesulfenyl chlorides HetSCl to alkenes, dienes, and acetylenes accompanied by the ring closure through the nitrogen atom of the HetS fragment.1—6 In particular, it was found that the reactions of 2 pyridinesulfenyl chlorides con taining substituents in the pyridine moiety even with rather readily transformable bicyclic olefins, such as norbornene3 and norbornadiene,6 afford exclusively cycloaddition products with retention of the carbon skeleton of the starting unsaturated compound. With the aim of extend ing the synthetic scope of this approach, in the present study we examined the possibility of performing the tandem rearrangement—cyclization reaction with the use of readily available tetrafluorobenzobarrelene (1)7,8 as the model substrate. The choice of diene 1 was determined by the fact that its reactions with various electrophilic reagents, including sulfenylating agents, involve cascade skeletal rearrangements.8—10

Fe-catalyzed chlorination of isothiocyanates (I) affords the previously unknown title compounds (II) in good yield.

The reactions of HetSCl, where Het = 4,6-dimethyl-2-pyrimidyl, 3-methoxycarbonyl-2-pyridyl, 1,3-benzothiazol-2-yl and 8-quinolyl, with a carbon–carbon multiple bond in the LiClO4–MeNO2 system lead to the formation of products of polar cycloaddition of sulfur-containing electrophile with ring closure by the nitrogen atom of the HetS fragment.