Convenient Synthesis of Ferrocenylethynyl Ketones via Carbonylative Coupling of Ferrocenylethyne with Aryl Iodides by Using Water as Solvent

Abstract

Carbonylative coupling reaction of aryl iodides with ferrocenylethyne catalyzed by PdCl 2 was carried out using sodium dodecyl sulphonate (SDS) as surfactant and water as solvent. The reaction gave much better yields of aryl ferrocenylethynyl ketones, which proceeded for 6 h at room temperature under a balloon pressure of carbon monoxide with Et 3 N as base.

Conjugated Ynones in Organic Synthesis

“…Furthermore, the synthesis of ferrocenylethynyl ketones 147 was performed using water as solvent under Cu-free conditions. 236 This carbonylative alkynylation has been carried out under PdCl 2 (5 mol %) and PPh 3 (10 mol %) catalysis at 1 atm of CO using sodium dodecyl sulfate (SDS) as surfactant and Et 3 N (3 equiv) as a base. The resulting ynones (147) were obtained in modest to good yields (10−84%).…”

“…This transformation requires the use of an equimolecular amount the copper(I) salt. 567 Yadav and co-workers reported on the reaction of electronrich arenes with ynones (71) catalyzed by gallium(III) chloride, which gave the corresponding (E)-enones (236) in good yield as the only product (Scheme 368). 568 α,α-Dibromoketones (224, easily obtained from ethyl acetylene carboxylates; Scheme 99, section 2.4.2) can be transformed into the corresponding silyl enol ethers (825) and 1-(1-alkynyl)-2,2-dibromovinyl acetates 826 in good yields (Scheme 369).…”

“… This process was also applied to the synthesis of flavones using 2-iodophenols. Furthermore, the synthesis of ferrocenylethynyl ketones 147 was performed using water as solvent under Cu-free conditions . This carbonylative alkynylation has been carried out under PdCl 2 (5 mol %) and PPh 3 (10 mol %) catalysis at 1 atm of CO using sodium dodecyl sulfate (SDS) as surfactant and Et 3 N (3 equiv) as a base.…”

Palladium-catalyzed carbonylative coupling reactions between Ar–X and carbon nucleophiles

“…42 In 2009, the same group reported another protocol for the synthesis of ferrocenylethynyl ketones in water. 43 The use of phosphites, e.g. P(OPh) 3 as a ligand in palladiumcatalyzed carbonylative Sonogashira coupling was first reported by Trzeciak and co-workers.…”

Palladium-catalyzed carbonylative Sonogashira coupling between aryl triazenes and alkynes

“…Notably, 3jl was obtained from ferrocenylethyne (2l) in 49% yield, which has some potential applications in photoactive semiconductors and liquid crystals. 18 More investigation on the substituent effect on both aryl triazenes and aryl alkynes was performed and we were glad to see that aryl iodide (1n) and bromides (1h, 1q, 2g) were well tolerated. These aryl halides could undergo further palladium-catalyzed crosscouplings to introduce various functional groups.…”