Computational Mechanistic Analysis of Intramolecular Cycloadditions of the 1,3-Dithiolium Cation with Adjacent Alkene and Allene Functional Groups

[Image: see text] In this work, the molecular mechanisms for the intramolecular cycloaddition reactions of the 1,3-dithiolium cation with adjacent alkenyl and allenyl groups were investigated by density functional theory calculations. Transition states for the mechanistic steps were searched, and their connections to corresponding reactive intermediates were validated by the intrinsic reaction coordinate method. Our studies demonstrate that both the alkenyl and allenyl groups can readily react with a neighboring 1,3-dithiolium cation first through a one-step asynchronous [3 + 2] cycloaddition path, with moderate activation energy barriers (ca. 20–30 kcal/mol) to overcome. Subsequent to the intramolecular dithiolium–alkene/allene cycloadditions, the resulting intermediates continue to undergo a series of reactions, including rearrangement, ring opening, and deprotonation to eventually yield the thermodynamically favored products, which carry a fused tricyclic molecular skeleton, 3,8-dihydro-2H-indeno[2,1-b]thiophene. Detailed geometric and energetic properties for all of the stationary points (transition states and intermediates) on the reaction potential surfaces have been calculated and examined. Key transition states and reactive intermediates were subjected to quantum theory of atoms in molecules and natural bonding orbital calculations to elucidate their bonding features and the stabilizing effects arising from orbital interactions. Finally, a comparative study using the continuum solvation model based on the charge density was conducted to evaluate the solvent effects on the intramolecular dithiolium–alkene/allene cycloadditions, which are the rate-limiting steps of the overall reactions. The results show that different organic solvents (polar and nonpolar) do not lead to much variations in the heights of activation energy barriers and hence indicate that solvent effects are actually insignificant on the reactions.