- Palladium-catalyzed thiocarbonylation of aryl, vinyl, and benzyl bromides
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(Chemical Equation Presented) A catalytic protocol for synthesis of thioesters from aryl, vinyl, and benzyl bromides as well as benzyl chlorides was developed using only stoichiometric amounts of carbon monoxide, produced from a solid CO precursor inside a two-chamber system. As a catalytic system, the combination of bis(benzonitrile) palladium(II) chloride and Xantphos furnished the highest yields of the desired compounds, along with the weak base, NaOAc, in anisole at 120°C. The choice of catalytic system as well as solvent turned out to be important in order to ensure a high chemoselectivity in the reaction. Both electron-rich and electron-deficient aryl bromides worked well in this reaction. Addition of 1 equiv of sodium iodide to the reaction improved the chemoselectivity with the electron-deficient aryl bromides. The thiol scope included both aryl and alkyl thiols, including 2-mercaptobenzophenones, whereby a thiocarbonylation followed by a subsequent McMurry coupling yielded differently substituted benzothiophenes. It was demonstrated that the methodology could be applied for 13C introduction into the thiophene ring.
- Burhardt, Mia N.,Ahlburg, Andreas,Skrydstrup, Troels
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p. 11830 - 11840
(2015/02/05)
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- Palladium-catalyzed thiocarbonylation of iodoarenes with thiols in phosphonium salt ionic liquids
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(Chemical Equation Presented) Trihexyl(tetradecyl)phosphonium hexafluorophosphate, a phosphonium salt ionic liquid (PSIL) is a particularly effective general reaction media for the Pd-catalyzed carbonylation reaction of iodoarenes and thiols to form thioesters. Recycling of the ionic liquid containing active Pd-catalyst was also demonstrated.
- Cao, Hong,McNamee, Laura,Alper, Howard
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p. 3530 - 3534
(2008/09/20)
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- REACTIONS OF ORGANOMETALLIC COMPOUNDS CATALYZED BY TRANSITION-METAL COMPLEXES. XV. PRODUCTION OF THIOCARBOXYLIC S-ESTERS BY CATALYTIC CARBONYLATION OF ARYL IODIDES AND TRIETHYLTIN THIOLATES
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Carbonylation in the aryl iodide-triethyltin thiolate system, catalyzed by bis(triphenylphosphine) palladium, was studied.In the case of unactivated aryl iodides containing weak electron-withdrawing substituents thiocarboxylic S-esters are formed with satisfactory yields.The reactions of aryl iodides containing strong electron-withdrawing groups lead mainly to the products from cross-coupling, i.e., unsymmetrical sulfides.The mechanism of the catalytic action of the phosphine complex of palladium was investigated.
- Gulevich, Yu. V.,Bumagin, N. A.,Beletskaya, I. P.
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p. 1918 - 1923
(2007/10/02)
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