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Yohsuke Yamamoto, Tohru Tsuchiya, Masahide Ochiumi, Shin-ichi Arai, Naoki Inamoto, Kin-ya Akiba, A Mechanistic Study on the Reaction of Iminothiadiazolines with Activated Acetylenes: Competitive Pathway through Hypervalent Sulfurane and Zwitterion, Bulletin of the Chemical Society of Japan, Volume 62, Issue 1, January 1989, Pages 211–218, https://doi.org/10.1246/bcsj.62.211
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Abstract
The reaction of 3-aryl-5-benzoyl-2-imino-2,3-dihydro-1,3,4-thiadiazoles (6) with dimethyl acetylenedicarboxylate (4b) gave the corresponding 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 [R=B/C] depended solely on the solvent polarity (ET). Dibenzoylacetylene behaved similarly. Several iminothiazolines and iminothiadiazolines 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.