Extracurricular laboratory:new discovery of 1,1′-Bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex

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Under anhydrous conditions, 4-phenyl-2H-chromenes were obtained in excellent yields by a cross-coupling reaction of 4-trifluoromethylsulfonyloxy-2H-chromenes with arylboronic acids, except for o-methoxyphenylboronic acid, in the presence of K2CO3 and several palladium catalysts. Although copper(I) iodide, used as a co-catalyst, showed no effect on this reaction, it was confirmed to act in the case of the coupling reaction of 4-trifluoromethylsulfonyloxy-2H-chromene with tributylphenyltin, instead of phenylboronic acid, in the presence of [Pd(PPh3)4].

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

Can You Really Do Chemisty Experiments About Bis(dibenzylideneacetone)palladium

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Herein, we report a Pd-catalysed alkoxycarbonylation of alkenes based on the use of a recyclable CO2 reduction product, the crystalline and air-stable N-formylsaccharin, as a CO surrogate. The carbonylation proceeds under ambient conditions in an exceptionally complementary regioselective fashion yielding the desired branched products from styrene derivatives and valuable linear esters from alkyl-substituted alkenes.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

More research is needed about Bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II)

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A concise synthesis of the biologically active alkaloid berberine is reported, and a versatile palladiumcatalyzed enolate arylation is used to form the isoquinoline core. The overall yield of 50%is a large improvement over the single, previous synthesis. By design, this modular route allows the rapid synthesis of other members of the protoberberine family (e.g., pseudocoptisine and palmatine) by substitution of the readily available aryl bromide and ketone coupling partners. Moreover, by combining enolate arylation with in situ functionalization, substituents can be rapidly and regioselectively introduced at the alkaloid C13 position, as demonstrated by the total synthesis of dehydrocorydaline. The avoidance of electrophilic aromatic substitution reactions to make the isoquinoline allows direct access to analogues possessing more varied electronic properties, such as the fluorine-containing derivative synthesized here.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

Properties and Exciting Facts About Bis(dibenzylideneacetone)palladium

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A two-step (nucleophilic substitution/palladation by oxidative addition) sequence provides a high-yielding access to a non-symmetrical palladium NNC pincer complex. A number of terminal and internal alkynoic acids with different substitution patterns at the alpha- and beta-positions are regio- and diastereoselectively cycloisomerized to the corresponding exocyclic enol lactones in the presence of exceedingly low amounts of the latter palladium complex, so that unprecedented turnover numbers and frequencies ranging from 1,000,000 to 700,000 and from 41,667 to 9722 h?1, respectively, are achieved. The optimized protocol, based on the use of a catalytic amount of triethylamine as base, allows an easy real-time monitoring of the reaction by NMR spectroscopy. Several pieces of evidence in favor of the direct participation of the above pincer complex as the catalyst of the reaction have been gathered from kinetic and poisoning experiments. (Figure presented.).

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Bench-stable solid triorganoindium compounds have been prepared by coordination with 4-(dimethylamino)pyridine (DMAP). The solid R3In(DMAP) complexes are obtained from the corresponding solution of R3In in quantitative yield and can be stored for up to several weeks. These reagents show excellent reactivity in palladium-catalyzed cross-coupling reactions with organic electrophiles.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

Awesome and Easy Science Experiments about Bis(benzonitrile)palladium chloride

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New Zn(ii), Cd(ii) and Hg(ii) complexes of saccharinate (sac) and 2,6-bis(2-benzimidazolyl)pyridine (bzimpy), [Zn(bzimpy)2](sac)2·2H2O (Zn), [Cd(sac)2(bzimpy)] (Cd) and [Hg(sac)2(bzimpy)] (Hg), were prepared and fully characterized by spectroscopic methods and X-ray crystallography.In vitroanticancer screening in A549 (lung), MCF-7 (breast) and HT29 (colon) cell lines showed thatZnwas highly cytotoxic against A549 and MCF-7 cells with IC50values of 1.74 ± 0.06 and 3.15 ± 0.10 muM, respectively, andHgdemonstrated potent cytotoxic activity in MCF-7 cells (8.61 ± 0.98 muM), whileCdand bzimpy exhibited moderate growth inhibitory activities in all of the cell lines. In addition, they showed significantly lower toxicity towards normal human breast epithelial MCF10A cells. Moreover, the complexes exhibited significantly high nuclease activity towards plasmid DNA and their interactions with DNA were assessed by gel electrophoresis and DNA docking.ZnandHginduced G0/G1 cell arrest and apoptotic cell death detectedviatypical DNA condensation/fragmentation, annexin V staining and caspase 3/7 activity in A549 and MCF-7 cells. These complexes further caused depolarization of mitochondria and oxidative damage of genomic DNA following excessive production of reactive oxygen species (ROS).

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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The catalytic synthesis of isobutanol (iBuOH), via the Guerbet condensation of methanol with n-propanol is described. In particular, bifunctional catalysts based on either heterogeneous or homogeneous dehydrogenating/hydrogenating palladium species and on sodium methoxide (MeONa) as basic component were investigated. When heterogeneous Pd/C and MeONa was used as catalytic system a high activity was obtained with turnover numbers up to about 110mol of iBuOH/(mol of Pd h). The increase of the MeONa/Pd molar ratio increased the activity of the catalyst. However, differently from Cu-based/MeONa catalysts, a significant metal leaching was observed; recycle experiments indicated that both heterogeneous and homogeneous palladium species are involved in the catalysis. When homogeneous palladium complexes, such as tetrakis(triphenylphosphine)palladium(0) [Pd(PPh3)4] diphenylphosphinoethane(dichloro)palladium(II) [Pd(dppe)Cl2] and bis(dibenzylideneacetone)palladium(0) [Pd(dba)2], were used in combination with MeONa a remarkable activity was also obtained, independently of the oxidation state of the palladium precursor. During the reaction deposition of a solid was observed and recycle experiments carried out both on the recovered solid and on the liquid phase suggested that also in this case the activity has to be addressed to both heterogeneous and homogeneous (or colloidal) palladium species.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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An enantioselective and branch-regioselective alpha-allylation of N-methyl anilines under dual palladium/photoredox catalysis is described. Readily available N-methyl anilines are used as formal “hard” alkyl nucleophiles without preactivation. Acetic acid is the only side product, which leads to a high atom economy of this reaction. This protocol shows good functional group tolerance and broad scope. A range of chiral homoallylic amines were prepared in moderate to good yields (up to 76%) and excellent regioselectivities (B:L > 95:5 in all cases) and enantioselectivities (up to 96% ee) under mild reaction conditions.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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N-Arylamido complexes of zirconium in which the amido functional group is attached to an o-(alkyliminoethyl) substituted aromatic ring, have been synthesised by salt elimination reactions and characterised by spectroscopic and diffraction methods; they are analogous to the N-silylamido species recently reported (Dalton Trans., 2002, 3290-3299). The ligands 2-[CyN=C(CH 3)]C6H4N(H)(xyl), LxylH, and 2-[CyN=C(CH3)]C6H4N(H)(mes) LmesH, Cy – C6H11, xyl = 3,5-Me2C6H 3 mes = 2,4,6-Me3C6H2, were prepared in good yields by Buchwald-Hartwig amination of the arylbromides with 2-[CyN=C(CH3)]C6H4NH2. Reaction of LmesLi with Zr(NEt2)2Cl2(thf) 2 gave after chloride substitution the arylamido ketimino complex LmesZr(NEt2)2Cl 1; variable amounts of the arylamido vinylamido complex 2 were also obtained. Interaction of L mesLi or LxylLi with Ti(NMe2) 2Cl2 gave rise to the tripodal bis-amido amino complexes 5 and 6 possibly formed by ligand rearrangement involving migration of the dimethylamido group to the ketimino carbon.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

Properties and Exciting Facts About 1,1′-Bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex

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The bis(diphenylphisphino)ferrocene (dppf) derived palladium analogue of [PdCl2(dppf)] on reaction with the sodium salt of pyridyl/pyrimidyl selenolate yielded mononuclear cis configured complex [Pd(SeAr)2(dppf)] (Ar = C5H4N, C4H(4,6-Me)2N2), as did the platinum precursor [PtCl2(dppf)] with methyl substituted pyrimidyl salt giving [Pt{SeC4H(4,6-Me)2N2}2(dppf)]. In contrast, the reaction of platinum precursor with the sodium salt of pyridylselenolate gave two different complexes [Pt2(mu-SeC5H4N)2(dppf)2]2+ and [Pt(Cl)(SeC5H4N)(dppf)] depending in the reaction solvent. These complexes were characterized by elemental analysis and NMR (1H, 31P) spectroscopy. The molecular structure of [Pt{SeC4H(4,6-Me)2N2}2(dppf)] was established by single crystal X-ray diffraction analysis.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method