Perfluorooxosulfate Salts as SOF4-Gas-Free Precursors to Multidimensional SuFEx Electrophiles
Armir Zogu
Department of Chemistry, Sustainable Chemistry for Metals and Molecules (SCM2), KU Leuven Department of Chemistry, Celestijnenlaan 200F—box 2404, B-3001 Leuven, Belgium
Search for more papers by this authorKarim Ullah
Department of Chemistry, Sustainable Chemistry for Metals and Molecules (SCM2), KU Leuven Department of Chemistry, Celestijnenlaan 200F—box 2404, B-3001 Leuven, Belgium
Department of Chemistry and Technologies of Drug, Sapienza, University of Rome, P.le A. Moro 5, 00185 Rome, Italy
Search for more papers by this authorStefanos Spanopoulos
Department of Chemistry, Sustainable Chemistry for Metals and Molecules (SCM2), KU Leuven Department of Chemistry, Celestijnenlaan 200F—box 2404, B-3001 Leuven, Belgium
Search for more papers by this authorCorresponding Author
Ermal Ismalaj
Department of Chemistry, Sustainable Chemistry for Metals and Molecules (SCM2), KU Leuven Department of Chemistry, Celestijnenlaan 200F—box 2404, B-3001 Leuven, Belgium
CIC biomaGUNE, Basque Research and Technology Alliance (BRTA), Paseo Miramon, 20014 San Sebastian, Guipuzcoa, Spain
CIBER de Enfermedades Respiratorias (CIBERES), 28029 Madrid, Spain
Search for more papers by this authorCorresponding Author
Wim M. De Borggraeve
Department of Chemistry, Sustainable Chemistry for Metals and Molecules (SCM2), KU Leuven Department of Chemistry, Celestijnenlaan 200F—box 2404, B-3001 Leuven, Belgium
Search for more papers by this authorCorresponding Author
Joachim Demaerel
Department of Chemistry, Sustainable Chemistry for Metals and Molecules (SCM2), KU Leuven Department of Chemistry, Celestijnenlaan 200F—box 2404, B-3001 Leuven, Belgium
Search for more papers by this authorArmir Zogu
Department of Chemistry, Sustainable Chemistry for Metals and Molecules (SCM2), KU Leuven Department of Chemistry, Celestijnenlaan 200F—box 2404, B-3001 Leuven, Belgium
Search for more papers by this authorKarim Ullah
Department of Chemistry, Sustainable Chemistry for Metals and Molecules (SCM2), KU Leuven Department of Chemistry, Celestijnenlaan 200F—box 2404, B-3001 Leuven, Belgium
Department of Chemistry and Technologies of Drug, Sapienza, University of Rome, P.le A. Moro 5, 00185 Rome, Italy
Search for more papers by this authorStefanos Spanopoulos
Department of Chemistry, Sustainable Chemistry for Metals and Molecules (SCM2), KU Leuven Department of Chemistry, Celestijnenlaan 200F—box 2404, B-3001 Leuven, Belgium
Search for more papers by this authorCorresponding Author
Ermal Ismalaj
Department of Chemistry, Sustainable Chemistry for Metals and Molecules (SCM2), KU Leuven Department of Chemistry, Celestijnenlaan 200F—box 2404, B-3001 Leuven, Belgium
CIC biomaGUNE, Basque Research and Technology Alliance (BRTA), Paseo Miramon, 20014 San Sebastian, Guipuzcoa, Spain
CIBER de Enfermedades Respiratorias (CIBERES), 28029 Madrid, Spain
Search for more papers by this authorCorresponding Author
Wim M. De Borggraeve
Department of Chemistry, Sustainable Chemistry for Metals and Molecules (SCM2), KU Leuven Department of Chemistry, Celestijnenlaan 200F—box 2404, B-3001 Leuven, Belgium
Search for more papers by this authorCorresponding Author
Joachim Demaerel
Department of Chemistry, Sustainable Chemistry for Metals and Molecules (SCM2), KU Leuven Department of Chemistry, Celestijnenlaan 200F—box 2404, B-3001 Leuven, Belgium
Search for more papers by this authorGraphical Abstract
Sulfurimidoyl difluorides (RNSOF2) are excellent multidimensional SuFEx hubs, however their preparation from the scarcely available thionyl tetrafluoride (SOF4) gas limits this chemistry. Here, we propose silver pentafluorooxosulfate (AgOSF5) as a viable alternative to SOF4. Prepared by the AgF2-mediated oxidation of SOCl2, we found that the adduct produces sulfurimidoyl fluorides in high yields from primary amines, also extendable to AgOSF4CF3.
Abstract
Sulfur(VI) Fluoride Exchange (SuFEx) chemistry stands as a well-established method for swiftly constructing complex molecules in a modular fashion. An especially promising segment of this toolbox is reserved for multidimensional SuFEx hubs: three or more substituents pluggable into a singular SVI centre to make ‘beyond-linear’ clicked constructions. Sulfurimidoyl difluorides (RNSOF2) stand out as the prime example of this, however their preparation from the scarcely available thionyl tetrafluoride (SOF4) limits this chemistry to only a few laboratories with access to this gas. In this work, we identify silver pentafluorooxosulfate (AgOSF5) as a viable SuFEx hub with reactivity equal to SOF4. The AgF2-mediated oxidation of SOCl2 gives rise to the hexacoordinate AgOSF5 adduct, which in contact with primary amines produces the sulfurimidoyl fluorides in high yields. In addition, we have found this workflow to be fully extendable to the trifluoromethyl homologue, AgOSF4CF3, and we propose the use of AgOSF4X salts as a general route to azasulfur SuFEx electrophiles from commercial starting materials.
Open Research
Data Availability Statement
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