63864-53-9Relevant articles and documents
Decarbonylative Suzuki-Miyaura Cross-Coupling of Aroyl Chlorides
Zhou, Tongliang,Xie, Pei-Pei,Ji, Chong-Lei,Hong, Xin,Szostak, Michal
supporting information, p. 6434 - 6440 (2020/09/02)
Herein, we report a catalyst system for Pd-catalyzed decarbonylative Suzuki-Miyaura cross-coupling of aroyl chlorides with boronic acids to furnish biaryls. This strategy is suitable for a broad range of common aroyl chlorides and boronic acids. The synthetic utility is highlighted in the direct late-stage functionalization of pharmaceuticals and natural products capitalizing on the presence of carboxylic acid moiety. Extensive mechanistic and DFT studies provide key insight into the reaction mechanism and high decarbonylative cross-coupling selectivity.
Oxidative addition step in reactions involving palladium activation of carbon-halogen and carbon-oxygen bonds
Shmidt,Smirnov
, p. 495 - 501 (2008/10/09)
Different modifications of the Heck reaction involving the activation of carbon-halogen and carbon-oxygen bonds by palladium (styrene phenylation with iodobenzene or benzoic anhydride and iodobenzene carbonylation, reductive coupling, and reduction) are studied by in situ 31P NMR spectroscopy. The catalytic cycles of the reactions include oxidative addition to Pd(0) formed in situ. The product composition in this step depends strongly on the composition of the reaction mixture, which is related to PhX conversion in the main catalytic process and with the nature of the catalyst precursor. A new hypothesis as to the mechanism of the catalytic cycle in alkene arylation in the presence of phosphine ligands is suggested. This hypothesis is consistent with NMR monitoring data and with the value of the kinetic isotope effect.
Reactions of free radicals with η3-allylpalladium(II) complexes: Phenyl and trityl radicals
Reid, Simon J.,Baird, Michael C.
, p. 3975 - 3980 (2007/10/03)
The compounds (η3-allyl)PdCl(PPh3) and [(η3-allyl)Pd(PPh3)2]Cl react with phenyl and trityl radicals generated from the thermal decomposition of phenylazotriphenylmethane (PhN=NCPh3, PAT) in benzene at 60°C. The products are the palladium phenyl compounds, [PdPhCl(PPh3)]2 and trans-PdPhCl(PPh3)2, respectively, and 4,4,4-triphenyl-1-butene, the latter being the result of coupling of the trityl radical with the allyl ligands. In contrast, [(η3-allyl)PdCl]2 reacts with phenyl and trityl radicals under the same conditions to form palladium metal, trityl chloride and 3-phenylpropene, which is subsequently catalytically isomerized to 1-phenylpropene. These disparate results are interpreted in all cases in terms of initial attack by phenyl radicals on the palladium(II) to give phenyl-palladium(III) intermediates, and it is the secondary reactions, influenced by the presence or absence of coordinated PPh3 ligands, which provide variety in the products. The reaction of [(4-methoxy-1,3-η3-cyclohexenyl)PdCl]2 gives a mixture of trans-3-methoxy-6-phenylcyclohexene and trans-4-methoxy-3-phenylcyclohexene, consistent with initial formation of a phenyl-palladium(III) intermediate followed by phenyl migration to the η3-cyclohexenyl ligand (reductive elimination).
