Amino Acid‐Based Dithiocarbamates as Efficient Intermediates for Diversity‐Oriented Synthesis of Thiazoles

Abstract

Amino acid‐based dithiocarbamates were introduced as efficient intermediates for the synthesis of a diverse library of novel di‐ and tri‐substituted thiazoles via condensation with various reagents such as anhydrides, acyl halides, benzene sulfonyl chloride, trifluoromethanesulfonic anhydride, chloroethyl formate, and diethyl chlorophosphate. The utilities of adducts in further organic synthesis were confirmed by Sonogashira and oxidation reactions. In addition, reaction of aspartic acid‐based dithiocarbamates with anhydrides affords the corresponding fused 6,6a‐dihydrofuro[3,2‐d]thiazol‐5(3aH)‐ones diastereoselectively in excellent yields.

Multicomponent synthesis of fully substituted thiazoles using glycine-based dithiocarbamates, acetic anhydride and nitroalkenes

“…Although the present study seems to be a combination of the two previous works (ref. 17 and 28), in comparison with the work of Wang et al ., which afforded the 2,4-disubstituted thiazolone derivatives, the results are completely different and fully substituted 1,3-thiazoles were obtained by a novel one-pot, three-component reaction. In addition, this new multicomponent reaction was performed under metal- and solvent-free conditions at comfortable temperatures to afford fully substituted thiazoles in high yields.…”

“…Dithiocarbamates are one of the most remarkable active intermediates in synthetic organic chemistry. 17,18 They play dual roles of electrophile and nucleophile in organic synthesis and have been applied successfully for the preparation of thioureas, 18 isothiocyanates, 19 cyanamides, 20 protected aldehydes, 21 and amides. 22 They have also found application as amine surrogates in the Betti reaction 23 and are useful in the protection of amino groups in peptide synthesis.…”

“…16 In addition, recently, we have discovered an efficient method for the synthesis of di- and tri-substituted 2-(alkysulfanyl)thiazoles via the condensation reaction of amino acid-based dithiocarbamates with various coupling reagents such as anhydrides, acyl halides, benzene sulfonyl chloride, trifluoromethanesulfonic anhydride, chloroethyl formate and diethyl chlorophosphate (Scheme 1a). 17 However, simple, green and innovative procedures for the synthesis of novel thiazoles with various substituent patterns are always in demand.…”

Catalyst free one pot three components synthesis of 2-iminothiazoles from nitroepoxides and thiourea

“…In continuation of our interest on the synthesis of N,S-heterocycles and the chemistry of nitroepoxides [49][50][51][52] , herein we report a novel catalyst-free one-pot three-component route for the synthesis of 2-imino-1,3-thiazolines via nitroepoxide ring opening reaction (Scheme 1f). Reaction of ethylamine 1 with phenyl isothiocyanate 2 and nitroepoxide 3a was considered as a model reaction for optimization of the reaction conditions.…”

Catalyst-Free One-Pot Three-Component Synthesis of 2-Iminothiazoles from Nitroepoxides

“…In continuation of our interest on the synthesis of N,S-heterocycles and the chemistry of nitroepoxides, [45][46][47][48] herein we report a novel catalyst-free one-pot three-component route for the synthesis of 2-imino-1,3thiazolines via nitroepoxide ring opening reaction (Scheme 1f). Reaction of ethylamine 1 with phenyl isothiocyanate 2 and nitroepoxide 3a was considered as a model reaction for optimization of the reaction conditions.…”