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

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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-3-phenyl-2-thiohydantoin gave a racemic product whereas the axially chiral 5-methyl-3-o-bromophenyl-2-thiohydantoin was less prone to racemize at C5 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 C5.

Graphical abstract: Elucidation of the atroposelectivity in the synthesis of axially chiral thiohydantoin derivatives

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Article information


Submitted
29 Nov 2019
Accepted
25 Jan 2020
First published
28 Jan 2020

Org. Biomol. Chem., 2020, Advance Article
Article type
Paper

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

Z. P. Haslak, S. Agopcan Cinar, S. Sarigul Ozbek, G. Monard, I. Dogan and V. Aviyente, Org. Biomol. Chem., 2020, Advance Article , DOI: 10.1039/C9OB02556A

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