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 H2O2-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.

Click Reaction of Selenols with Isocyanates: Rapid Access to Selenocarbamates as Peroxide-Switchable Reservoir of Thiol-Peroxidase-Like Catalysts / Antonella Capperucci, Alessandra Petrucci, Cristina Faggi, Damiano Tanini. - In: ADVANCED SYNTHESIS & CATALYSIS. - ISSN 1615-4169. - ELETTRONICO. - 363:(2021), pp. 4256-4263. [10.1002/adsc.202100611]

Click Reaction of Selenols with Isocyanates: Rapid Access to Selenocarbamates as Peroxide-Switchable Reservoir of Thiol-Peroxidase-Like Catalysts

Antonella Capperucci;Cristina Faggi;Damiano Tanini
2021

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 H2O2-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.
363
4256
4263
Antonella Capperucci, Alessandra Petrucci, Cristina Faggi, Damiano Tanini
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2158/1243635
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