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Keywords:

  • aminophosphines;
  • C[BOND]C bond formation;
  • Heck cross-coupling;
  • nanoparticles;
  • palladium

Abstract

The palladium-based dichlorobis[1-(dicyclohexylphosphanyl)piperidine] complex – [(P{(NC5H10)(C6H11)2})2Pd(Cl)2] is readily prepared in quantitative yield from the reaction of [Pd(cod)(Cl)2] (cod=cycloocta-1,5-diene) with two equivalents of 1-(dicyclohexylphosphanyl)piperidine in toluene under N2 within only a few minutes at room temperature. This complex is a highly active Heck catalyst with excellent functional group tolerance, which reliably operates at low catalyst loadings. Various activated, non-activated, deactivated, functionalized, sterically hindered, and heterocyclic aryl bromides, which may contain nitro, chloro or trifluoromethane groups, nitriles, acetales, ketones, aldehydes, ethers, esters, lactones, amides, anilines, phenols, alcohols, carboxylic acids, and heterocyclic aryl bromides, such as pyridines and derivatives, as well as thiophenes and aryl bromides containing methylsulfanyl groups have been successfully coupled with various (also functionalized) alkenes in excellent yields and selectivities (the E-isomers are typically exclusively formed) at 140 °C in the presence of 0.05 mol % of the catalyst in DMF. Even though lower catalyst loadings could be used for many electronically activated, non-activated and some electronically deactivated aryl bromides without noticeable loss of activity, the great advantage of the reaction protocol presented here lies in its reliability and general applicability, which allows its direct adoption to other aryl bromides without the neccessity of its modification. Experimental observations indicated that palladium nanoparticles are the catalytically active form. Consequently, whereas comparable levels of activity were observed for dichloro-bis(aminophosphine) complexes of palladium, a dramatic drop in activity was found for their phosphine-based analogue [(P(C6H11)3)2Pd(Cl)2].