%0 Journal Article %T Anomalous reactivity of benzopinacolone towards 4-phenylthiosemicarbazide, a nucleophile endowed with alpha-effect %J Journal of Medicinal and Chemical Sciences %I Sami Publishing Company (SPC) %Z 2651-4702 %A Kassehin, Urbain C. %A Adjibode, Steeve A. %A Bautista, Oscar %A Gbaguidi, Fernand A. %A Quetin- Leclercq, Joëlle %A McCurdy, Christopher R. %A Frédérick, Raphaël %A Poupaert, Jacques H. %D 2019 %\ 01/01/2019 %V 2 %N 1 %P 17-20 %! Anomalous reactivity of benzopinacolone towards 4-phenylthiosemicarbazide, a nucleophile endowed with alpha-effect %K Benzopinacolone %K Green chemistry %K N-thiobenzoyl-thiosemicarbazide %K Photochemistry %K Trypanocidal chemotherapeutic %R 10.26655/jmchemsci.2019.6.3 %X In a medicinal chemistry-driven drug discovery program aimed at synthesizing new topically-acting trypanocidal chemotherapeutic agents to treat the African trypanosomiasis, our research group became interested in new chemical entities bearing in their center a thiohydrazide (C=S) NHNH or thiosemicarbazide NH(C=S) NHNH central template flanked on both sides by lipophilic aryl moieties. In this context, benzopinacolone was found to react as a rather unusual acylating agent via a mechanism (addition/elimination) involving addition of the nucleophile (a thiosemicarbazide derivative), formation of a resulting tetrahedral adduct, and expulsion of a trityl anion moiety as leaving group, presumably through an anchimeric assistance effect by intram-olecular participation of the thioureido side-chain via hydrogen bond formation. The present incidental discovery should be considered at this level as a first inception and further work is now being directed at closely examining the detailed mechanism of this exceptional chemical pathway; in a reaction involving the unusual breaking of a carbon-carbon bond (carbon acid as leaving group) in the rate-determining step and involving the decomposition of the intermediate tetrahedral adduct to get the final unexpected N-thiobenzoyl-thiosemicarbazide. %U https://www.jmchemsci.com/article_69027_5639c2a37b9cf2b4101af076433bfb07.pdf