A Mechanistic Study on the Reaction of Iminothiadiazolidines with Activated Acetylenes: Competitive Pathway through Hypervalent Sulfurane and Zwitterion

Article abstract of DOI:10.1246/bcsj.62.211

The reaction of 3-aryl-5-benzoyl-2-imino-2,3-dihydro-1,3,4-thiadiazoles (6) with dimethyl acetylenedicarboxylate (4b) gave the correspinding thiazole (8) and benzoyl cyanide through sulfurane (B) by 1,3-dipolar cycloaddition and cis-(9) and trans-vinyl (10) compounds through zwitterion (C) by simple addition.Two types of addition reactions competed each other and the ratio of the two depended solely on the solvent polarity (R_τ).Dibenoylacetylene behaved similarly.Several iminothiazolines iminithiadiazolidines reacted with activated acetylenes and the selectivity for the two types of addition reactions for each system was shown to be affected by quite subtle balance of electron-withdrawing ability of each heterocycle.