Sulfur dichloride reactions with dienes

A unique reaction for the preparation of a fused cyclic system containing the thietane ring is the addition of sulfur dichloride to norbornadicne to give 93. This reaction, however, failed to produce similar results with other cyclic 1,4-dienes. 

The reaction of sulfur dichloride with cyclic dienes has been extended to cyclic polyolefins.5 The reagent reacts with cyclooctatetraene (5) to give (6) as the major product. The reaction is of interest because additions to cyclooctatetraene usually... 

Transannular addition of sulfur dichloride to 9-azabicyclo[3.3.1]nona-2,6-dienes (42 N-formyl 9l 44 N-phenylsulfonyl 94 and 62 N-tolylsulfonyl p 3i, 32)j applied as an entry to the 2-thia-6-aza-adamantane system. The chlorine atoms in 91 were easily exchangeable with sodium iodide in boiling diethyl ketone (-> 92, 82%)" or with silver acetate in acetic acid (- 93, 70%)" resp. Under analogous reaction conditions the dichloride 94 was transformed into the diacetate 95 (95%) " LiAlH4-reduction of the diacetate 93 yielded 74% of N(6)-methyl-4 8 -dihydroxy-2-thia-6-aza-adamantane (97). The C(4) and C(8)... 

The reaction of sulfur dichloride with dienes can produce cyclic or polymeric produas, depending upon experimental conditions. To prepare... 

The product 303 from disulfur dichloride and 2,3-dimethylbuta-l,3-diene rearranges spontaneously to the tetrahydrothiophene 304 (equation 159)150. The reaction of liquid sulfur dioxide with conjugated dienes 305 (e.g. butadiene, isoprene) results in cyclic sulfones which dissociate into their components on heating (equation 160)151 152. 

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