Arenesulfonyl Fluoride Synthesis via Copper‐free Sandmeyer‐type Fluorosulfonylation of Arenediazonium Salts

Abstract

Summary of main observation and conclusion The limited availability of highly valuable arenesulfonyl fluorides seriously hinders their further application in many research fields including medicinal chemistry and chemical biological, organic synthesis, polymer preparation, etc. We report herein a mild and efficient copper‐free Sandmeyer‐type fluorosulfonylation reaction of various arenediazonium salts to prepare valuable arenesulfonyl fluorides using K2S2O5 as both a reductant and a practical sulfonyl source in combination with N‐fluorobenzenesulfonimide as an effective fluorine source. This methodology provides an attractive route to diverse important arenesulfonyl fluorides given the overall practicality and scope.

Sulfonyl fluorides as targets and substrates in the development of new synthetic methods

“…In 2020, Chen and Liu reported the Sandmeyertype fluorosulfonylation using arenediazonium salts, a copper(II) catalyst, DABSO (a SO2 surrogate) and KHF2, which is an inexpensive nucleophilic fluoride source 71 (eq 15). Later, it was found similar reactivity could be achieved with copper-free methods [72][73][74] , or by the use of an organic photoredox catalyst 75 . An attractive feature of these methods is that they commence with non sulfur-containing substrates, and instead introduce the sulfonyl (-SO2 -) unit from SO2 surrogates.…”

Synthetic strategies for fluorosulfonylated compounds: application to click chemistry reactions

“…At the same time that the report by Lin appeared, Liu and colleagues 51 introduced a variant of the work of Qing, this time employing K 2 S 2 O 5 as the source of SO 2 and NFSI as the F atom provider, in MeCN/H 2 O/HOAc and benzenediazonium tetrafluoroborates as starting substrates. The reactions were carried out at room temperature for 6 h, and the yields of products were comparable to those of the other two methodologies.…”

Visible-light-initiated external photocatalyst-free synthesis of α,α-difluoro-β-ketoamides from 4-aminocoumarins

“…2 Among the reported fluorinating reagents, N -fluorobenzenesulfonimide (NFSI) is one of the most easily available and versatile reagents, and has been widely applied in organic transformations including fluorination, amination, sulfonylation, and oxidation reactions. 3…”