Atroposelective Synthesis of Axially Chiral Thiohydantoin Derivatives

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In conclusion, we have investigated the sequential sulfonylation/desulfination reaction of 5-(4-hydroxylbenzyl)-thiohydantoin with excess arylsulfonyl chloride in the presence of triethylamine. These reactions are operationally simple and proceed smoothly under very mild reaction conditions, providing a broad range of 5-arylidene thiohydantoin derivatives in moderate to excellent yields. The further applications of the reaction in the synthesis of biologically relevant molecules are ongoing in our laboratory. The bioassay showed that these compounds exhibit certain fungicidal activities with the 71.9% inhibition rate of 2K against B. cinerea, and 57.6% inhibition rate of 2m against A. solani, respectively.

Sheikh and Yulu Zhang}, title = {Full Paper A Simple Synthesis of 2-Thiohydantoins†}, year = }

Synthesis of Thiohydantoin Tryptophan Derivatives ..

T1 - 5,5-Diphenyl-2-thiohydantoin-N10 (DPTH-N10) suppresses proliferation of cultured colon cancer cell line COLO-205 by inhibiting DNA synthesis and activating apoptosis

Copper complexes of thiohydantoin series were synthesized as possible anticancer drugs

Thiohydantoin derivatives of tryptophan have been identified as moderate inhibitors of the enzyme IDO. One synthetic pathway of these enzyme inhibitors begins with the synthesis of glycine thiohydantoin derivatives from glycine methyl ester and isothiocyanate. The glycine thiohydantoin derivative is then reacted with indole-3-carboxaldehyde derivatives to form a dehydro product which is reduced to form the desired thiohydantoin derivative and potential inhibitor.

the synthesis of glycine thiohydantoin ..

Design and synthesis of indoline thiohydantoin …

A novel method for the liquid-phase combinatorial synthesis of 3-substituted-2-thiohydantoin has been developed using poly (ethylene glycol)-supported isothiocyanate. The PEG-supported isothiocyanate was obtained from the reaction of PEG with bromoacetyl bromide (20), followed by an Aza-Wittig reaction. Reaction of PEG-supported isothiocyanate with various aliphatic amines and carbon disulfide (phenyl ethylamine (21)) offered 3-substituted 2-thiohydantoins (22) in excellent yields with addition, cyclization and cleavage reactions occurring in one pot (Scheme 8) ().

Facile Synthesis of 5-Arylidene Thiohydantoin by ..

Nonracemic axially chiral thiohydantoins were synthesized atroposelectively by the reaction of -aryl isothiocyanates with amino acid ester salts in the presence of triethylamine (TEA). The synthesis of the nonaxially chiral derivatives, however, gave thiohydantoins racemized at C-5 of the heterocyclic ring. The micropreparatively resolved enantiomers of the nonaxially chiral derivatives from the racemic products were found to be optically stable under neutral conditions. On formation of the 5-methyl-3-arylthiohydantoin ring, bulky -aryl substituents at N3 were found to suppress the C-5 racemization and in this way enabled the transfer of chirality from the α-amino acid to the products. The corresponding 5-isopropylthiohydantoins turned out to be more prone to racemization at C-5 during the ring formation. The isomer compositions of the synthesized axially chiral thiohydantoins have been determined through HPLC analyses with chiral stationary phases. In most cases a high prevalence of the P isomers over the M isomers has been obtained. The barriers to rotation determined around the Nsp2–Caryl chiral axis were found to be dependent upon the size of the -halo aryl substituents.

A simple synthesis of 2-thiohydantoins. - Semantic …

A practical and ecofriendly synthesis of 3-alkyl-5-dimethyaminomethylidene-2-thioxo-imidazolidin-4-one derivatives from 2-thiohydantoins was reported by without the use of any solvent. The preparation of 3- alkyl-5-dimethylaminomethylene-2-thioxo-imidazolidin- 4-ones (43) was reported by the reaction between 3-substituted-2-thioxo-imidazolidin-4-ones (42), alkyl and aryl isothiocyanates and methyl glycinate hydrochloride (41) in basic medium. The reactivities of 2-thioxo-imidazolidin-4-ones derivatives (42) with N, N-dimethylformamide diethylacetal (DMF-DEA) using solvent-free conditions under was investigated by the research group. The 2-thioxo-imidazolidin-4-ones (42) were converted with DMF-DEA (1.05 equiv.) into the corresponding 5-dimethylaminomethylidene-2-thioxo-imidazolidin-4-ones (43) in yields ranging from 74 to 77% after a reaction time of around 30 min at 70-80°C (Scheme 13) ().