Click Reaction of Selenols with Isocyanates: Rapid Access to Selenocarbamates as Peroxide‐Switchable Reservoir of Thiol‐Peroxidase‐Like Catalysts. Issue 17 (14th July 2021)

• Record Type: Journal Article
• Authors: Capperucci, Antonella; Petrucci, Alessandra; Faggi, Cristina; Tanini, Damiano
• Is Part Of: Advanced synthesis & catalysis. Volume 363:Issue 17(2021)
• Page Start: 4256
• Page End: 4263
• Publication Date: 2021-07-14
• Subjects: Selenocarbamates -- Selenols -- Isocyanates -- Antioxidants -- Glutathione peroxidase-like catalysts; Catalysis -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Chemistry -- Periodicals; Chemistry, Technical -- Periodicals; Chemistry -- Periodicals; Catalysis -- Periodicals; Technology, Pharmaceutical -- Periodicals; 547.2
• DOI: 10.1002/adsc.202100611
• Languages: English
• ISSNs: 1615-4150

Abstract

Abstract: Selenols react with isocyanates under mild catalyst‐free conditions to generate selenocarbamates in good yield and with high selectivity over potentially competing nucleophilic additions. The methodology enables the incorporation of a wide variety of functional groups providing access to a broad array of densely functionalised selenocarbamates. In the presence of competing heteroatom‐centered nucleophiles, isocyanates selectively couple with selenols. Selenocarbamates exhibited thiol‐peroxidase‐like properties, enabling the reduction of hydrogen peroxide at the expense of thiols, which are converted into the corresponding disulfides. A series of control experiments suggested that the catalytic mechanism proceeds through a pathway, involving a H2 O2 ‐promoted transcarbamoylation reaction leading to a thiocarbamate with concomitant releasing of catalytically active selenolate anions. By undergoing peroxide‐driven thiol‐selenol exchange, selenocarbamates behave as equivalents of selenolate anions with thiol‐peroxidase‐like activity. Abstract :