Elucidation of the atroposelectivity in the synthesis of axially chiral thiohydantoin derivatives - Université de Lorraine Access content directly
Journal Articles Organic & Biomolecular Chemistry Year : 2020

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

Zeynep Pinar Haslak
  • Function : Author
Sesil Agopcan Cinar
  • Function : Author
Sevgi Sarigul Ozbek
  • Function : Author
Ilknur Dogan
  • Function : Author
  • PersonId : 1101971
Viktorya Aviyente
  • Function : Author

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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hal-03259112 , version 1 (14-06-2021)

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Zeynep Pinar 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 & Biomolecular Chemistry, 2020, 18, pp.2233 - 2241. ⟨10.1039/c9ob02556a⟩. ⟨hal-03259112⟩
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