Unprecedented Reactivity of AgSCF<inf>3</inf> with o-Isocyanobiaryls: Synthetic and Mechanistic Insight
Issued Date
2023-01-01
Resource Type
ISSN
21935807
Scopus ID
2-s2.0-85166322665
Journal Title
Asian Journal of Organic Chemistry
Rights Holder(s)
SCOPUS
Bibliographic Citation
Asian Journal of Organic Chemistry (2023)
Suggested Citation
Phetcharawetch J., Betterley N.M., Hassa N., Witayapaisitsan N., Leowanawat P., Soorukram D., Reutrakul V., Surawatanawong P., Kuhakarn C. Unprecedented Reactivity of AgSCF<inf>3</inf> with o-Isocyanobiaryls: Synthetic and Mechanistic Insight. Asian Journal of Organic Chemistry (2023). doi:10.1002/ajoc.202300271 Retrieved from: https://repository.li.mahidol.ac.th/handle/20.500.14594/88264
Title
Unprecedented Reactivity of AgSCF<inf>3</inf> with o-Isocyanobiaryls: Synthetic and Mechanistic Insight
Author's Affiliation
Other Contributor(s)
Abstract
The work reports an unusual reaction of o-isocyanobiaryls and AgSCF3, which led to the unexpected formation of 6-(trifluoromethyl)phenanthridines and o-biaryl isothiocyanates as products, instead of the expected 6-((trifluoromethyl)thio)phenanthridines. Density functional theory (DFT) calculations on the relative free energy of β-fragmentation and 6-endo-trig radical cyclization pathways of the key thioimidoyl radical intermediate suggested that β-fragmentation of the S−CF3 bond is preferable, releasing CF3 radical and o-biaryl isothiocyanate. The CF3-imidoyl intermediate arising from the addition of CF3 radical to o-isocyanobiaryl then underwent 6-endo-trig radical cyclization to provide 6-(trifluoromethyl)phenanthridines. This work demonstrates the alternate application of AgSCF3 in generating trifluoromethylated and isothiocyanate products.