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Elucidation of the atroposelectivity in the synthesis of axially chiral thiohydantoin derivatives

Abstract : Recently, Sarigul and Dogan have synthesized a number of enantiomerically enriched axially chiral atropoisomeric 2-thiohydantoins by the reaction of L-amino acid ester salts and o-aryl isothiocyanates in the presence of triethyl amine (TEA) in dichloromethane. The non-axially chiral derivative 5-methyl-3phenyl-2-thiohydantoin gave a racemic product whereas the axially chiral 5-methyl-3-o-bromophenyl-2-thiohydantoin was less prone to racemize at C 5 of the heterocyclic ring. In this study, we present a computational study (M06-2X/6-311+G(d,p) for C, H, O, N and S; M06-2X/6-311++G(3df,3pd) for Br) in order to propose plausible mechanisms for the racemization and cyclization steps for 2-thiohydantoin derivatives. The study includes rationalization based on steric as well as the electrostatic effects to elucidate the epimerization differences at C 5. † Electronic supplementary information (ESI) available. See
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https://hal.univ-lorraine.fr/hal-03259112
Contributor : Gérald Monard <>
Submitted on : Monday, June 14, 2021 - 2:10:51 PM
Last modification on : Tuesday, June 15, 2021 - 3:20:01 AM

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Zeynep Haslak, Sesil Agopcan Cinar, Sevgi Sarigul Ozbek, Gérald Monard, Ilknur Dogan, et al.. Elucidation of the atroposelectivity in the synthesis of axially chiral thiohydantoin derivatives. Organic and Biomolecular Chemistry, Royal Society of Chemistry, 2020, 18, pp.2233 - 2241. ⟨10.1039/c9ob02556a⟩. ⟨hal-03259112⟩

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