Decarboxylative arylation with diaryliodonium(iii) salts: alternative approach for catalyst-free difluoroenolate coupling to aryldifluoromethyl ketones

Abstract

Catalyst‐free access to aryldifluoromethyl ketones has been achieved through decarboxylative arylation of α,α‐difluoro‐β‐ketoacid salts using diaryliodonium(III) salts. The products were successfully transformed into the corresponding esters, amides, and difluoromethyl compounds....

Auxiliary strategy for the general and practical synthesis of diaryliodonium(III) salts with diverse organocarboxylate counterions

“…Electron-rich aryl ligands derived from anisole, mesitylene, and particularly 1,3,5trimethoxybenzene are highly recommended for chemoselective arylation processes. Aryl(TMP)iodonium(III) salts have been successfully used as transition metal-free arylating reagents for various nucleophiles such as nitrogen- [23][24][25][26], oxygen- [13,[27][28][29], sulfur- [30], and carbon- [31] nucleophiles due to their excellent reactivity and aryl group selectivity over aryl(anisyl)iodonium(III) salts [32] and aryl(mesityl)iodonium(III) salts [33].…”

Decarboxylative Aldol Reaction of α,α-Difluoro-β-keto Esters: Easy Access to Difluoroenolate

“…4b Yield 96% (143.0 mg), colorless solid, mp 96.5−97.0 °C (from Et 2 O−C6). 1 H NMR (400 MHz, CDCl 3 ) δ 8.06 (d,J = 8.4 Hz,2H),1H),4H),7.36 (d,J = 8.4 Hz,2H),5.36 (dd,J = 18.8,5.0 Hz, 1H), 3.18 (brs, 1H); 13 C{ 1 H} NMR (100 MHz, CDCl 3 ) δ 190.7 (dd, J = 31.8, 28.9 Hz), 135.0,134.8,133.1,132.2 (m),130.3 (m),129.5,128.7,128.5,115.4 (dd,J = 264.9,257.2 Hz), 72.6 (dd, J = 28.9, 23.1 Hz); 19 6 (dd,J = 31.8,29.9 Hz),166.8,139.6,134.8,132.1 (m),130.6,130.3 (m),129.5,128.7,128.2,115.5 (dd,J = 265.9,257.2 Hz), 72.8 (dd, J = 27.9, 23.1 Hz), 52.2; 19 F NMR (376 MHz, CDCl 3 ) δ −103.9 (dd, J = 296.0, 5.2 Hz, 1F), −116.4 (dd, J = 296.0, 19.2 Hz,1F). MS m/z = 320 [M + ]; HRMS (EI): m/z [M + ] calcd for C 17 H 14 F 2 O 4 : 320.0860; found: 320.0866.…”

“…4 The synthesis of difluoromethylene compounds using decarboxylation has been expanded to include the introduction of an aryl group. 5 In this study, the decarboxylation method was expanded to include a wide range of skeletal transformations. Decarboxylation reactions are environmentally friendly chemical transformations that only involve the release of CO 2 .…”

“…The synthesis of difluoromethylene compounds using decarboxylation has been expanded to include the introduction of an aryl group . In this study, the decarboxylation method was expanded to include a wide range of skeletal transformations.…”

Silver-Catalyzed Coupling of Unreactive Carboxylates: Synthesis of α-Fluorinated O-Aryl Esters

“…11b,17 By contrast, the reaction of α,α-difluoro-βketo acid sodium salt underwent decarboxylative ligand coupling to afford α-aryl-α,α-difluoromethyl aryl ketones. 18 Here, we describe the unprecedented O-arylation of αfluorinated carboxylic acid salts with TMP-iodonium salts, affording various fluorine-containing O-aryl esters. To the best of our knowledge, this is the first example of combining a silver salt with a diaryliodonium salt that enables arylation.…”