1,3-dithiolanes from cycloadditions of alicyclic and aliphatic thiocarbonyl ylides with thiones: regioselectivity

The regiochemistry of 1,3-dithiolanes obtained from thiocarbonyl ylides 9 and thiones 10 shows a striking dependence on substituents. Previously and newly performed experiments indicate that sterically hindered cycloalkanethione S-methylides and dialkylthioketone S-methylides react with alicyclic and aliphatic thiones to give the 2,2,4,4-tetrasubstituted 1,3-dithiolanes 11 exclusively. Aryl groups in one or both reactants lead to a preference for, or even complete formation of, 4,4,5,5-tetrasubstituted 1,3-dithiolanes 12. Several mechanisms appear to be involved, but the paucity of experimental criteria is troubling. Quantum-chemical calculations (see preceding paper) on the cycloaddition between thioacetone S-methylide and thioacetone furnish lower activation energies for the concerted process than for the two-step pathways via C,S- or C,C-biradicals; the favoring of the 2,4-substituted 1,3-dithiolanes over the 4,5-substituted type would be expected to increase with growing bulk of substituents. Aryl groups stabilize intermediate biradicals. Experimental criteria for the differentiation of regioisomeric dithiolanes are discussed. Thiocarbonyl ylides 9 are prepared by 1,3-cycloadditions between diazomethane and thioketones and subsequent N(2) elimination from the usually isolable 2,5-dihydro-1,3,4-thiadiazoles 17; different ratios of the two rate constants lead to divergent product formation scenarios.