CuI-Catalyzed Fluorodesulfurization for the Synthesis of Monofluoromethyl Aryl Ethers

Abstract

An efficient CuI-catalyzed fluorodesulfurization for the synthesis of monofluoromethyl aryl ethers using DAST at room temperature has been developed. This approach exhibits a good functional group tolerance, a broad substrate scope, and a high synthesis efficiency.

Fluoromethoxymethylation of Nitrogen Heterocyclic Compounds with Fluoromethyl Iodide

“…8 In the same year, Wu and co-workers discovered an approach for the synthesis of monofluoromethyl benzyl ethers by using CuI as a catalyst and DAST as a fluoride source. 9 However, all of these indirect methods reported limited substrate scope. In addition, Shen's group disclosed two monofluoromethyl-substituted sulfonium ylides that reacted with a series of primary alcohols to give the fluoromethoxymethylated products.…”

“…In 2017, Maycock’s group synthesized several fluoromethoxymethylated compounds from alcohols using nonvolatile ( S )-alkyl-( S )-phenyl-2,3,4,5-tetramethylphenylsulfonium triflate and sodium hydride . In the same year, Wu and co-workers discovered an approach for the synthesis of monofluoromethyl benzyl ethers by using CuI as a catalyst and DAST as a fluoride source . However, all of these indirect methods reported limited substrate scope.…”

[4 + 2] cycloaddition reactions of β-naphtha-1-thioquinones generated from 2-naphthols and DAST

“…Our research originated from an accidental discovery. In our previous work, DAST and a difluorocarbene precursor were used for O -monofluoromethylation 17 and O -difluorodeuterated methylation 18 of phenols. Out of curiosity, 2-naphthol, DAST and BrCF 2 PO(OEt) 2 were mixed together to see if it would be possible to perform an O -trifluoromethylation reaction.…”

Direct and Chemoselective Electrophilic Monofluoromethylation of Heteroatoms (O-, S-, N-, P-, Se-) with Fluoroiodomethane

“…Pleasingly, the technique could be applied to chemoselectively fluoromethylate aromatic alcohols in the presence of various decorating elements such as halogens ( 8 – 10 ), ester ( 11 ), nitrile ( 12 ), ethers 13 , ketones ( 14 – 15 ), and aldehydes ( 16 – 17 ) (Scheme ). Notably, sterically hindered ( 18 ) and (hetero)­polyaromatic systems ( 19 − 20 ) acted as competent partners for the reaction, as well as an allyl-presenting phenol ( 21 ).…”