Five-membered heterocyclic rings are abundant in natural products and pharmaceuticals. Thus, continued investigation of new heterocyclic ring forming reactions are of interest to the synthetic community. 2-Imidazolidinethiones, 2-imidazolidinones, and 2-iminoimidazolidines have found a diverse array of biological applications. For example, 2-imidazolidinethiones have shown analgesic, antiserotonin, and herbicidal activity, while 2-imidazolidinones have shown anticancer activity and the ability to inhibit various enzymes, among them HIV protease. 2-Iminoimidazolidines have shown analgesic and antiparasitic activity. Current synthetic access to these scaffolds is as varied as their biological activity. Based on a recent report of Cu-catalyzed S-vinylation with N-(2-bromoallyl)butylamine and CS2, it was hypothesized that additional heteroallenes of the general format R-Y=C=Z, namely isothiocyanates, isocyanates, and carbodiimides, could undergo similar heteroatom-vinylation to access 4-methylene-2-imidazolidinethiones, 4-methylene-2-imidazolidinones, and 4-methylene-2-iminoimadazolidines, respectively. Preliminary results show that N-(2-bromoallyl)butylamine reacts readily with phenyl isothiocyanate in the presence of CuI to form the resulting 4-methylene-2-imidazolidinethione. In the absence of CuI, the reaction stalls at the acyclic thiourea. Progress on the investigation of Cu-catalyzed heteroatom-vinylation between N-(2-bromoallyl)butylamine and isothiocyanates, isocyanates, and carbodiimides will be reported. Optimization of reaction conditions, catalyst screening, and substrate scope will be detailed. Additionally, the potential for a mixture of products based on regiochemistry of the ring formation and rearrangement of the exocyclic methylene will be addressed. This previously unreported reaction will enhance synthetic access to these important heterocycles.

Cu-catalyzed heteroatom-vinylation for synthesis of 2-imidazolidinethiones, 2-imidazolidinones, and 2-iminoimidazolidines

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

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