Ex situ Generation of Thiazyl Trifluoride (NSF3) as a Gaseous SuFEx Hub**
Bing-Yu Li
Sustainable Chemistry for Metals and Molecules (SCM2), Department of Chemistry, KU Leuven, Celestijnenlaan 200F, Box 2404, 3001 Leuven, Belgium
Search for more papers by this authorKexin Su
Biomolecular Architecture, Department of Chemistry, KU Leuven, Celestijnenlaan 200F, PO Box 2404, 3001 Leuven (Heverlee), Belgium
Search for more papers by this authorProf. Dr. Luc Van Meervelt
Biomolecular Architecture, Department of Chemistry, KU Leuven, Celestijnenlaan 200F, PO Box 2404, 3001 Leuven (Heverlee), Belgium
Search for more papers by this authorProf. Dr. Steven H. L. Verhelst
Laboratory of Chemical Biology, Department of Cellular and Molecular Medicine, KU Leuven, O&N I bis, Herestraat 49, box 901, 3000 Leuven, Belgium
Leibniz Institute for Analytical Sciences ISAS, e.V., Otto-Hahn-Str. 6b, 44227 Dortmund, Germany
Search for more papers by this authorDr. Ermal Ismalaj
Sustainable Chemistry for Metals and Molecules (SCM2), Department of Chemistry, KU Leuven, Celestijnenlaan 200F, Box 2404, 3001 Leuven, Belgium
CIC biomaGUNE, Basque Research and Technology Alliance (BRTA) Paseo Miramon, 20014 San Sebastian, Guipuzcoa, Spain
Search for more papers by this authorCorresponding Author
Prof. Dr. Wim M. De Borggraeve
Sustainable Chemistry for Metals and Molecules (SCM2), Department of Chemistry, KU Leuven, Celestijnenlaan 200F, Box 2404, 3001 Leuven, Belgium
Search for more papers by this authorCorresponding Author
Dr. Joachim Demaerel
Sustainable Chemistry for Metals and Molecules (SCM2), Department of Chemistry, KU Leuven, Celestijnenlaan 200F, Box 2404, 3001 Leuven, Belgium
Laboratory of Chemical Biology, Department of Cellular and Molecular Medicine, KU Leuven, O&N I bis, Herestraat 49, box 901, 3000 Leuven, Belgium
Search for more papers by this authorBing-Yu Li
Sustainable Chemistry for Metals and Molecules (SCM2), Department of Chemistry, KU Leuven, Celestijnenlaan 200F, Box 2404, 3001 Leuven, Belgium
Search for more papers by this authorKexin Su
Biomolecular Architecture, Department of Chemistry, KU Leuven, Celestijnenlaan 200F, PO Box 2404, 3001 Leuven (Heverlee), Belgium
Search for more papers by this authorProf. Dr. Luc Van Meervelt
Biomolecular Architecture, Department of Chemistry, KU Leuven, Celestijnenlaan 200F, PO Box 2404, 3001 Leuven (Heverlee), Belgium
Search for more papers by this authorProf. Dr. Steven H. L. Verhelst
Laboratory of Chemical Biology, Department of Cellular and Molecular Medicine, KU Leuven, O&N I bis, Herestraat 49, box 901, 3000 Leuven, Belgium
Leibniz Institute for Analytical Sciences ISAS, e.V., Otto-Hahn-Str. 6b, 44227 Dortmund, Germany
Search for more papers by this authorDr. Ermal Ismalaj
Sustainable Chemistry for Metals and Molecules (SCM2), Department of Chemistry, KU Leuven, Celestijnenlaan 200F, Box 2404, 3001 Leuven, Belgium
CIC biomaGUNE, Basque Research and Technology Alliance (BRTA) Paseo Miramon, 20014 San Sebastian, Guipuzcoa, Spain
Search for more papers by this authorCorresponding Author
Prof. Dr. Wim M. De Borggraeve
Sustainable Chemistry for Metals and Molecules (SCM2), Department of Chemistry, KU Leuven, Celestijnenlaan 200F, Box 2404, 3001 Leuven, Belgium
Search for more papers by this authorCorresponding Author
Dr. Joachim Demaerel
Sustainable Chemistry for Metals and Molecules (SCM2), Department of Chemistry, KU Leuven, Celestijnenlaan 200F, Box 2404, 3001 Leuven, Belgium
Laboratory of Chemical Biology, Department of Cellular and Molecular Medicine, KU Leuven, O&N I bis, Herestraat 49, box 901, 3000 Leuven, Belgium
Search for more papers by this authorA previous version of this manuscript has been deposited on a preprint server (https://doi.org/10.26434/chemrxiv-2023-l4ztm).
Graphical Abstract
Here we report a synthetic procedure for the efficient ex situ generation of thiazyl trifluoride gas (N≡SF3) as a new Sulfur(VI)-Fluoride Exchange hub. In typical SuFEx fashion, this triple-bonded azasulfur(VI) fluoride reagent and its mono-substituted derivatives react highly effectively with various nucleophiles to deliver a library of unreported thiazynes.
Abstract
Sulfur(VI)-fluoride exchange (SuFEx) chemistry, an all-encompassing term for substitution events that replace fluoride at an electrophilic sulfur(VI), enables the rapid and flexible assembly of linkages around a SVI core. Although a myriad of nucleophiles and applications works very well with the SuFEx concept, the electrophile design has remained largely SO2-based. Here, we introduce S≡N-based fluorosulfur(VI) reagents to the realm of SuFEx chemistry. Thiazyl trifluoride (NSF3) gas is shown to serve as an excellent parent compound and SuFEx hub to efficiently synthesize mono- and disubstituted fluorothiazynes in an ex situ generation workflow. Gaseous NSF3 was evolved from commercial reagents in a nearly quantitative fashion at ambient conditions. Moreover, the mono-substituted thiazynes could be extended further as SuFEx handles and be engaged in the synthesis of unsymmetrically disubstituted thiazynes. These results provide valuable insights into the versatility of these understudied sulfur functionalities paving the way for future applications.
Conflict of interest
The authors declare no conflict of interest.
Open Research
Data Availability Statement
The data that support the findings of this study are available in the Supporting Information of this article.
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