107271-15-8Relevant articles and documents
Progress in the Palladium-Catalyzed α-Arylation of Ketones with Chloroarenes
Ehrentraut, Andreas,Zapf, Alexander,Beller, Matthias
, p. 209 - 217 (2002)
Non- and deactivated chloroarenes can be coupled with a wide range of ketones to yield the corresponding arylmethyl ketones in good to excellent yields using a palladium(II) acetate/n-BuPAd2 catalyst system. Depending on the ketone, the chloroarene/ketone ratio and the base, mono or diarylation can be effected selectively.
α-arylation of ketones using highly active, air-stable (DtBPF)PdX2 (X = Cl, Br) catalysts
Grasa, Gabriela A.,Colacot, Thomas J.
, p. 5489 - 5492 (2007)
α-Arylation of various ketones with aryl chlorides and bromides using the well-defined and air-stable (DtBPF)PdX2 (X = Cl, Br) catalysts gave 80-100% yield of the coupled products under relatively mild conditions at low catalyst loadings. The X
Experimental and theoretical approaches to the influence of the addition of pyrene to a series of Pd and Ni NHC-based complexes: Catalytic consequences
Valds, Hugo,Poyatos, Macarena,Ujaque, Gregori,Peris, Eduardo
, p. 1578 - 1588 (2015)
A series of Ni and Pd complexes with three different N-heterocyclic carbene (NHC)-based ligands (imidazolylidene, benzimidazolylidene and pyrene-imidazolylidene) has been prepared and fully characterized. The influence of the addition of pyrene to solutions containing these complexes is studied by means of NMR and UV/Vis spectroscopies and by cyclic voltammetry. The addition of pyrene to the pyrene-NHC-containing Pd and Ni complexes gives rise to the formation of adducts by π-π stacking interactions between pyrene and the pyrene group of the NHC ligand. This interaction causes a modification of the electronic properties of the metal, as demonstrated by cyclic voltammetric studies of the Ni-NHC complexes. Theoretical calculations support this type of π-interactions, and justify the higher interactions observed with the pyrene-NHC containing complexes. The catalytic activities of the complexes were tested in the Suzuki-Miyaura C-C coupling and in the α-arylation of ketones. The addition of pyrene as an external π-stacking additive does not affect the activities of the complexes in the Suzuki-Miyaura coupling, but this observation may be justified due to the fact that the process is heterogeneously catalyzed, as indicated by the mercury-drop test. The addition of pyrene to the catalytic α-arylation of ketones results in a decrease in the activity of the reactions catalyzed by the pyrene-imidazolylidene palladium complex, whereas the other two catalysts do not modify their activity in the presence of this π-stacking additive.
Simple, highly active palladium catalysts for ketone and malonate arylation: Dissecting the importance of chelation and steric hindrance
Kawatsura, Motoi,Hartwig, John F.
, p. 1473 - 1478 (1999)
A remarkably active catalyst system for α-arylation of ketones and malonates was developed by proposing that sterically hindered alkylphosphines would accelerate the catalytic reaction rates. We initially tested the bisphosphine ligand D'BPF (1,1'-bis-(di-tert-butylphosphino)ferrocene) for this palladium-catalyzed chemistry. This catalyst system led to fast reaction rates for reactions of aryl bromides with ketones, including room temperature chemistry in many cases. In some cases turnover numbers were 20 000. The catalyst also gave mild reactions with aryl chlorides with yields that were similar to the chemistry with aryl bromides. Independent synthesis of the arylpalladium enolate complexes with isobutyrophenone enolate showed that only one phosphorus of the bisphosphine ligand D'BPF was coordinated in the enolate complex. Thus, we tested sterically hindered alkylphosphine ligands for the ketone and malonate arylation process and found that P(t-Bu)3 gave exceptionally fast rates and high turnover numbers for these reactions. These results demonstrate several principles for the catalytic chemistry that we did not anticipate: palladium complexes of monophosphine ligands can activate aryl chlorides under mild conditions, and palladium enolates coordinated by certain monophosphines can undergo C-C bond-forming reductive elimination much faster than β-hydrogen elimination.
Structural, Computational, and Spectroscopic Investigation of [Pd(κ3-1,1′-bis(di-tert-butylphosphino)ferrocenediyl)X]+ (X = Cl, Br, I) Compounds
Blass, Brittany L.,Hernández Sánchez, Raúl,Decker, Victoria A.,Robinson, Michael J.,Piro, Nicholas A.,Kassel, W. Scott,Diaconescu, Paula L.,Nataro, Chip
, p. 462 - 470 (2016)
The reaction of [Pd(dtbpf)Cl2] (dtbpf = 1,1′-bis(di-tert-butylphosphino)ferrocene) with sodium bromide yields [Pd(dtbpf)Br][Br], which displays an interaction between the iron and palladium atoms. The structure of this compound has been obtained and is compared to those of the previously reported [Pd(dtbpf)X]+ (X = Cl, I) analogues. Similar to [Pd(dtbpf)Cl]+, [Pd(dtbpf)Br]+ appears to undergo a solid-state isomerization at low temperature to a species in which the Fe-Pd interaction is disrupted. In addition to 1H and 31P{1H} NMR and visible spectroscopy, the [Pd(dtbpf)X]+ (X = Cl, Br) compounds were also characterized by zero-field 57Fe M?ssbauer spectroscopy. DFT calculations on [Pd(dtbpf)X]+ (X = Cl, Br, I) show that the Fe-Pd interaction is weak and noncovalent and that the strength of the interaction decreases as the halide becomes larger. A related trend is noted in the potential at which oxidation of the iron center occurs; the larger the halide, the less positive the potential at which oxidation occurs. Finally, the catalytic activity of [Pd(dtbpf)X]+ (X = Cl, Br, I) in the arylation of an aromatic ketone was examined and compared to the activity of [Pd(dtbpf)Cl2].
N-heterocyclic carbene-palladium complexes [(NHC)Pd(acac)Cl]: Improved synthesis and catalytic activity in large-scale cross-coupling reactions
Marion, Nicolas,De Fremont, Pierre,Puijk, Iris M.,Ecarnot, Elise C.,Amoroso, Dino,Bell, Andrew,Nolan, Steven P.
, p. 2380 - 2384 (2007)
From two commercially available starting materials, improved one-step, multigram-scale syntheses of [(IPr)Pd(acac)Cl] [IPr = N,N′-bis(2,6- diisopropylphenyl)imidazol-2-ylidene ; acac = acetylacetonate] and [(IMes)Pd(acac)Cl] [IMes=N,N′-bis(2,4,6-trimethyl
Blue Light Promoted Difluoroalkylation of Aryl Ketones: Synthesis of Quaternary Alkyl Difluorides and Tetrasubstituted Monofluoroalkenes
Li, Kangkui,Chen, Jingchao,Yang, Chunhui,Zhang, Keyang,Pan, Chunxiang,Fan, Baomin,Fan, Baomin
supporting information, p. 4261 - 4265 (2020/06/04)
A facile and cost-effective method for the preparation of fluoroalkylated compounds has been described by the direct photoexcitation of halofluoroalkanes with blue light absorptivity, enabling the difluoroalkylation of aryl ketones. The methodology has provided an efficient, mild, and catalyst-free synthetic method for quaternary difluoroalkylated arenes and tetrasubstituted monofluoroalkenes.
Palladate Precatalysts for the Formation of C-N and C-C Bonds
Zinser, Caroline M.,Warren, Katie G.,Nahra, Fady,Al-Majid, Abdullah,Barakat, Assem,Islam, Mohammad Shahidul,Nolan, Steven P.,Cazin, Catherine S. J.
, p. 2812 - 2817 (2019/08/12)
A series of imidazolium-based palladate precatalysts has been synthesized and the catalytic activity of these air- and moisture-stable complexes evaluated as a function of the nature of the imidazolium counterion. These precatalysts can be converted under
