Anomalous reactivity of benzopinacolone towards 4-phenylthiosemicarbazide, a nucleophile endowed with alpha-effect
Journal Title: Journal of Medicinal and Chemical Sciences - Year 2019, Vol 2, Issue 1
Abstract
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.
Authors and Affiliations
Urbain C. Kassehin, Steeve A. Adjibode, Oscar Bautista, Fernand A. Gbaguidi, Joëlle Quetin- Leclercq, Christopher R. McCurdy, Raphaël Frédérick, Jacques H. Poupaert
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- EP ID EP491186
- DOI 10.26655/JMCHEMSCI.2019.6.3
- Views 169
- Downloads 0
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