A mild and efficient synthesis of various aryl sulfonyl fluorides from diaryliodonium salts under organophotocatalysis 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 KHF 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.
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http://dx.doi.org/10.1039/d3ob01200j | DOI Listing |
Angew Chem Int Ed Engl
December 2024
Department of Applied Chemistry, Anhui Province Engineering Laboratory for Green Pesticide Development and Application, and Anhui Province Key Laboratory of Crop Integrated Pest Management, Anhui Agricultural University, Hefei, 230036, China.
An efficient enantioselective coupling reaction between sulfenamides and cyclic diaryliodonium salts is established via adaptive Cu/anionic stereogenic-at-Co(III) complex combined catalysis, precisely synthesizing a broad range of axially chiral sulfilimines with excellent enantioselectivities, diastereoselectivities, regioselectivities, and chemoselectivities (67 examples under same conditions, up to 98 % ee). The following thermodynamically controlled pyramidal inversion enables efficient stereodivegent synthesis of all four stereoisomers. Mechanistic studies suggest that anionic stereogenic-at-cobalt(III) complexes serve as counteranions of diaryliodonium and anionic ligand of Cu(I) catalyst simultaneously, which could be regarded as an explanation for outstanding selectivities.
View Article and Find Full Text PDFChem Commun (Camb)
December 2024
Institute for Organic and Analytical Chemistry, University of Bremen, Leobener Straße 7, 28359 Bremen, Germany.
A diverse set of hydroxy-benzo[]iodadioxaphosphinine oxides and derived diaryl iodonium salts are prepared and two examples are characterized by X-ray crystallography, featuring an out-of-plane geometry of the hypervalent bond for both compound classes. Treatment of the phosphate-stabilized diaryliodonium salts with Ca(OH) results in an efficient base-induced intramolecular aryl migration under aqueous conditions, yielding iodo-substituted diaryl ethers with yields up to 94%. Our findings highlight the synthetic potential of this previously underexplored compound class in organic transformations.
View Article and Find Full Text PDFBeilstein J Org Chem
November 2024
Department of Chemistry, SAS, Vellore Institute of Technology Chennai, Chennai-600 127, Tamil Nadu, India.
Diaryliodonium salts have become widely recognized as arylating agents in the last two decades. Both, symmetrical and unsymmetrical forms of these salts serve as effective electrophilic arylating reagents in various organic syntheses. The use of diaryliodoniums in C-C and carbon-heteroatom bond formations, particularly under metal-free conditions, has further enhanced the popularity of these reagents.
View Article and Find Full Text PDFJ Org Chem
December 2024
Graduate School of Pharmaceutical Sciences, Ritsumeikan University, 1-1-1, Nojihigashi, Kusatsu Shiga 525-8577, Japan.
Herein, we report the development of metal-free one/two-pot procedures for the synthesis of benzo[]isoxazol-3(1)-one (benzisoxazolone) heterocycles by designing diaryliodonium salts featuring -ester or nitrile functional groups. These react smoothly with protected hydroxylamines under mild conditions to produce -arylhydroxylamine intermediates, which readily cyclize to give benzisoxazolone derivatives under acidic conditions. This metal-free process maintains the weak N-O bond, tolerates a wide range of diaryliodonium salts and protected hydroxylamines with diverse functional/protecting groups, thereby overcoming the challenges associated with previous transformations.
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