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Synthesis 2023; 55(12): 1893-1903
DOI: 10.1055/a-2013-5801
DOI: 10.1055/a-2013-5801
paper
Metal-Free Cascade Synthesis of 1,2,4-Thiadiazoles from β-Ketothioamides and Alkyl/Aryl Cyanides under TBN Enabling Conditions at Room Temperature
We gratefully acknowledge the financial support from the Science and Engineering Research Board, New Delhi (CRG/2019/000058 and a JC Bose National Fellowship, JCB/2020/000023). The authors SS and SR are thankful to the University Grants Commission (UGC), New Delhi, for fellowships. We also acknowledge the support of the Department of Science and Technology, Ministry of Science and Technology, India (DST-FIST program) for basic and high-end analytical facilities to the department.
Abstract
A metal-free radical cascade cyclization of β-ketothioamides and alkyl/aryl cyanides has been developed for the synthesis of 1,2,4-thiadiazoles bearing a stable nitroso group at an exocyclic double bond in a one-pot system. The reaction proceeds via the in situ generated ketoxime intermediate of β-ketothioamide, which further assists the formation of 1,2,4-thiadiazole through reaction with nitrile under TBN (tert-butyl nitrite) mediation. The basic utility of this reaction is the formation of three new bonds (two C–N and one S–N) in one stretch under mild conditions. Moreover, this protocol features excellent functional group tolerance, operational simplicity, and easy scalability. The radical process is supported by the BHT adduct of the α-ketoxime intermediate. Noteworthy is that the products possess Z stereochemistry with regard to the exocyclic C=C double bond at the 5-position.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2013-5801.
- Supporting Information
Publication History
Received: 08 December 2022
Accepted after revision: 16 January 2023
Accepted Manuscript online:
16 January 2023
Article published online:
16 February 2023
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