Sulfur- and Amine- Promoted Multielectron Autoredox Transformation of Nitromethane: Multicomponent Access to Thiourea Derivatives
Issued Date
2023-01-01
Resource Type
ISSN
09476539
eISSN
15213765
Scopus ID
2-s2.0-85179335809
Journal Title
Chemistry - A European Journal
Rights Holder(s)
SCOPUS
Bibliographic Citation
Chemistry - A European Journal (2023)
Suggested Citation
Phaenok S., Nguyen L.A., Soorukram D., Nguyen T.T.T., Retailleau P., Nguyen T.B. Sulfur- and Amine- Promoted Multielectron Autoredox Transformation of Nitromethane: Multicomponent Access to Thiourea Derivatives. Chemistry - A European Journal (2023). doi:10.1002/chem.202303703 Retrieved from: https://repository.li.mahidol.ac.th/handle/123456789/91531
Title
Sulfur- and Amine- Promoted Multielectron Autoredox Transformation of Nitromethane: Multicomponent Access to Thiourea Derivatives
Other Contributor(s)
Abstract
Thiourea derivatives are in-demand motifs in organic synthesis, medicinal chemistry and material science, yet redox methods for the synthesis that start from safe, simple, inexpensive and readily available feedstocks are scarce. In this article, we disclose the synthesis of these motifs using elemental sulfur and nitromethane as the starting materials. The method harnesses the multi-electron auto-redox property of nitromethane in the presence of sulfur and amines, delivering thiourea products without any added oxidant or reductant. Extension of this reaction to cyclizable amines and/or higher homologues of nitromethane led to a wide range of nitrogen heterocycles and thioamides. Operationally simple, the reactions are scalable, tolerate a wide range of functional groups, and can be employed for the direct functionalization of natural products. Mechanistically, the nitro group was found to act as an oxidant leaving group, being reduced to ammonia whereas sulfur, along with the role of a sulfur building block for the thiocarbonyl group, behaved as a complementary reductant, being oxidized to sulfate.