On the Behavior of α,β-Unsaturated Thioaldehydes and Thioketones in the Diels−Alder Reaction

Alpha,beta-unsaturated thioaldehydes and thioketones, R1CH=CH-C(=S)R2, are prepared in situ by the reaction between the corresponding carbonyl compounds and bis(dimethylaluminum) sulfide. These compounds undergo [4 + 2] self-dimerization reactions in which one molecule serves as the heterodiene component and the other as the dienophile to afford different types of dimeric products depending on the R1 and R2: 1,2-dithiin and 1,3-dithiin (R1 = R2 = H), 1,2-dithiin (R1 = Ph, R2 = H, CH3), or dihydrothiopyran (R1 = R2 = Ph). These differences in selectivity are explained on the basis of the relative energies evaluated by molecular orbital (MO) calculations at the DFT (density functional theory) level. The calculations show that in the dimerization reaction of thioacrolein (I), the head-to-tail (S-C-S bonded) dimers are kinetically more stable by about 5 kcal/mol but slightly thermodynamically unstable by about 2 kcal/mol than the head-to-head (S-S bonded) dimers. The calculations on thiocinnamaldehyde (IV) indicate that the dimerization reactions of phenyl-substituted alpha,beta-unsaturated thioaldehydes and thioketones are almost equally controlled by thermodynamic and kinetic factors. These unsaturated thiocarbonyl compounds also function as heterodienes (C=C-C=S) in the cycloaddition reaction with norbornadiene and as dienophiles (C=S) in the reaction with cyclopentadiene.