Regioselektive 1,3-Dipolare Cycloadditionen eines ‘Thiocarbonyl-methanids’ ((Alkylidensulfonio)methanids) mit aromatischen Sulfinen

Regioselective 1,3-Dipolar Cycloadditions of a ‘Thiocarbonyl-methanide’ ((Alkylidenesulfonio)methanide) with Aromatic Sulfines Reaction of the spirocyclic 2,5-dihydro-1,3,4-thiadiazole 7 and thiobenzophenone S-oxide ( 6a ) in THF at 45° yielded the spirocyclic 1,3-dithiolane 1-oxide 8 , thiirane 9 , and the diazane derivative 10 in a ratio of 61:15:23 (Scheme 2). The formation of 8 is rationalized by a 1,3-dipolar cycloaddition of ‘thiocarbonyl-methanide’ 1 , generated from 7 by thermal elimination of N₂, and the C?S bond of sulfine 6a . Cyclization of intermediate 1 leads to thiirane 9 . Under the same conditions, 7 and adamantane-2-thione S-oxide ( 6b ) or 2,2,4,4-tetramethyl-3-thioxocyclobutanone S-oxide ( 4 ) reacted to give only 9 and 10 but no cycloadduct of type 8 (Scheme 4). With the aim to favor the formation of 8 , a mixture of 6a and 1.1 equiv. of 7 was heated to 45° without any solvent in a sealed tube. The ratio of products was only slightly different from that of the thermolysis in THF. An analogous experiment with 7 and 9H-fluorene-9-thione S-oxide ( 6c ) yielded cycloadduct 13 and 9 (Scheme 5). It is most interesting that the 1,3-dipolar cycloadditions of 1 and the sulfines 6a and 6c proceeded with different regioselectivity. A reaction mechanism for the unexpected formation of 10 is proposed in Scheme 7. The key step is the base-catalyzed ring opening of 7 and the nucleophilic addition of the thereby formed thiolate 21 onto the sulfonium ion 19 .