ABSTRACT
We disclose herein a photocatalytic decarboxylative fluorosulfonylation reaction of various hypervalent iodine(III) carboxylates in combination with 1,4-diazabicyclo[2.2.2]octane-bis(sulfur dioxide) adduct as a sulfonyl source and KHF2 as a desirable fluorine source via a radical sulfur dioxide insertion and fluorination strategy. A one-pot photocatalytic decarboxylative fluorosulfonylation reaction of various carboxylic acids mediated by PhI(OAc)2 was realized, as well. Notably, this transformation can be performed under heating conditions without the need for catalysts.
ABSTRACT
A mild and efficient synthesis of various aryl sulfonyl fluorides from diaryliodonium salts under organophotocatalysis via a radical sulfur dioxide insertion and fluorination strategy is presented. Diaryliodonium salts are used as aryl radical precursors, the 1,4-diazabicyclo[2.2.2]octane bis(sulfur dioxide) adduct (DABSO) as a sulfonyl source and cheap KHF2 as a desirable fluorine source, respectively. Notably, the electronic properties of substituents on the aromatic rings in diaryliodonium salts have a significant influence on the reaction yields.
ABSTRACT
We developed an efficient palladium-catalyzed fluorosulfonylation reaction of aryl thianthrenium salts to smoothly prepare various aryl sulfonyl fluorides using cheap Na2S2O4 as a convenient sulfonyl source in combination with N-fluorobenzenesulfonimide (NFSI) as an ideal fluorine source under mild reduction conditions. A one-pot synthesis of aryl sulfonyl fluorides starting from various arenes was established as well without the need for separating aryl thianthrenium salts. The practicality of this protocol was demonstrated by gram-scale synthesis, derivatization reactions, and excellent yields.
