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

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Design and synthesis of flavonoidal ethers and their anti-cancer activity in vitro

Flavonoids are well-characterized polyphenolic compounds with pharmacological and therapeutic activities. However, most flavonoids have not been developed into clinical drugs, due to poor bioavailability. Herein, we report a strategy to increase the drugability of flavonoids by constructing C(sp2)-O bonds and stereo- as well as regioselective alkenylation of hydroxyl groups of flavonoids with ethyl-2,3-butadienoate allenes. Twenty-three modified flavonoid derivatives were designed, synthesized, and evaluated for their anti-cancer activities. The results showed that compounds 4b, 4c, 4e, 5e, and 6b exhibited better in vitro inhibitory activity against several cancer cell lines than their precursors. Preliminary structure-activity relationship studies indicated that, in most of the cancer cell lines evaluated, the substitution on position 7 was essential for increasing cytotoxicity. The results of this study might facilitate the preparation or late-stage modification of complex flavonoids as anti-cancer drug candidates.

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

Extracurricular laboratory:new discovery of 32005-36-0

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Xanthene-phosphole ligands: Synthesis, coordination chemistry, and activity in the palladium-catalyzed amine allylation

Two new xanthene-phosphole derivatives, 3 and 4, were synthesized through the nucleophilic substitution of the cyano group in 1-P-cyano-2,5- diphenylphosphole (1) and 1-P-cyano-3,4-dimethylphosphole (2) by the 4,5-dilithium salt of 9,9?-dimethylxanthene. For this, a new synthetic procedure was developed, allowing the synthesis of the required 1-P-cyano-2,5-diphenylphosphole from the 1,2,5-triphenylphosphole. Both ligands (DPP-Xantphos 3 for the diphenyl derivative and DMP-Xantphos 4 for the dimethyl derivative) react with [Pd(allyl)Cl]2 to afford the corresponding cationic complexes 5Cl and 6Cl. Using AgOTf, stable triflate complexes 5OTf and 6OTf could be isolated. The chloride complexes, on the other hand, exhibit a limited stability in solution. The DPP-Xantphos derivative SCl eliminates allyl chloride to yield the dimeric palladium(O) complex 7 of general formula [Pd(3)]2, in which each palladium is coordinated to the two phosphorus atoms of the same ligand and to one double bond of one phosphole unit of the second ligand. Decomposition of complex 6Cl furnished a mixture of compounds featuring a dimeric trinuclear species of general formula [Pd 3(4)2Cl2]. This complex was also synthesized directly. Reaction of the DMP-Xantphos ligand 4 with 1 equiv of [Pd(COD)Cl 2] and 2 equiv of [Pd(dba)2] afforded dimer 8, which features one 18-VE Pd0 center and two Pd-Cl fragments, which are coordinated to the dienic system of the two phosphole ligands and connected through a single Pd-Pd bond. The catalytic activity of the triflate complexes 5OTf and 6OTf was evaluated in the allylation of aniline. Whereas the DMP-Xantphos derivative 6OTf exhibited a poor catalytic activity, very good conversion yields were obtained with the DPP-Xantphos complex 5OTf. On the basis of X-ray structure data and DFT calculations, it was concluded that the high catalytic activity of the DPP-Xantphos derivative complex [Pd(allyl)3]-[OTf] (6OTf) results from the combination of two effects: a large P-Pd-P bite angle, which enhances the reactivity of the allyl ligand, and the strong pi-accepting capacity of the diphenylphosphole moiety, which allows the easy formation of a 14-VE complex.

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

The important role of 32005-36-0

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Efficient and selective Palladium-catalyzed Telomerization of 1,3-Butadiene with Carbon Dioxide

A more efficient telomerization of 1,3-butadiene with carbon dioxide leading to the valuable delta-lactone 1 (3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one) is reported. The key to success is the use of a palladium/TOMPP-catalyst system (TOMPP=tris-(o-methoxyphenyl)-phosphine), which provided under optimal conditions significantly increased yields of the desired product and improved catalyst turnover numbers (TON=1500).

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

Extended knowledge of Bis(dibenzylideneacetone)palladium

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Process for preparing ortho-substituted phenylphosphine ligands

Ligand synthesis methods for the preparation of ligands having the formula wherein Q is selected from phosphorus, arsenic and antimony; wherein X1, X2 and X3 are carbon anions; and, wherein R15 is selected from -SO3, -SO2N(R18), -CO2, -PO3, -AsO3, -SiO2, -C(CF3)2O; where R18 is selected from a hydrogen, a halogen, a hydrocarbyl group and a substituted hydrocarbyl group, are disclosed. Also disclosed are methods of complexing the ligands with late transition metals to form catalyst complexes that catalyze polymerization reactions and/or Heck coupling reactions.

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

Discovery of Bis(dibenzylideneacetone)palladium

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In heterogeneous catalysis, the catalyst is in a different phase from the reactants. Quality Control of Bis(dibenzylideneacetone)palladium, At least one of the reactants interacts with the solid surface in a physical process called adsorption in such a way. 32005-36-0, name is Bis(dibenzylideneacetone)palladium. In an article£¬Which mentioned a new discovery about 32005-36-0

Palladium-catalyzed allylic substitution at four-membered-ring systems: Formation of eta1-allyl complexes and electrocyclic ring opening

Caught in the act: A series of unique eta1-allyl palladium complexes of four-membered cyclic systems bearing beta-hydrogens were prepared (see structure). Their unusual structure, reactivity, and unprecedented propensity for undergoing pericyclic reactions were uncovered. Copyright

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

Top Picks: new discover of Bis(dibenzylideneacetone)palladium

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Selective arylation and vinylation at the alpha position of vinylarenes

In intermolecular Heck reactions of styrene and vinylarenes, the aryl and vinyl groups routinely insert at the beta position. However, selective insertion at the alpha position has been very rare. Herein, we provide a missing piece in the palette of Heck reaction, which gave >20:1 alpha selectivity. The key to our success is a new ferrocene 1,1?-bisphosphane (dnpf) that carries 1-naphthyl groups. Our mechanistic studies revealed that the high alpha selectivity is partly attributable to the steric effect of dnpf. The rigid and bulky 1-naphthyl groups of dnpf sterically disfavor beta insertion. What the Heck! In intermolecular Heck reactions, insertion at the beta position of aromatic olefins is very common, but reversal of the selectivity for selective alpha insertion has been a longstanding problem. A general method to couple aryl and vinyl triflates with aromatic olefins in >20:1 alpha selectivity is presented. The key to this successful approach is a new ferrocene bisphosphane with naphthyl groups on the phosphorus atom (see scheme; OTf=triflate). Copyright

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Reference£º
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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Syntheses of palladated aryldithioacetals. Unexpected rearrangement involving C-S and C-Pd bonds

The reaction of C6HI(OMe)3-2,3,4- CH(STo)2-6 (1) (To = 4-tolyl) with [Pd(dba)2] (dba = dibezylideneacetone) at room temperature gives [Pd2{kappa2-C,S-CH(STo)(C6H(STo-2) (OMe)3-3,4,5)2 (mu-I)2] (3) or, in the presence of Tl(OTf) (OTf = CF3SO3) and bpy (2,2?-bipyridine), the cationic cyclopalladated complex [Pd{kappa2-C,S-C6H(OMe)3-2,3,4- CH(STo)2-6}(bpy)]OTf (2). 3 reacts with Tl(OTf) and (i) RNC (1:2:4) to give cis-[Pd{kappa2-C,S-CH(STo){C6H(STo-2) (OMe)3-3,4,5}}-CNR)2]OTf [R = 2,6-dimethylphenyl (4), tBu (4?)] or (ii) bpy to give an isometric form of 2, cis-[Pd{kappa2-C,S-CH(STo){C6H(STo-2)(OMe)3- 3,4,5}}(bpy)]OTf (5). The last reaction can be reversed by reacting 5 with NaI. The compound 2 reacts with NaI to give [Pd(C6H(OMe)3- 2,3,4-(CH(STo)2-6)I(bpy)] (6), which can be also prepared by reaction of 1 with [Pd(dba)2] in the presence of bpy. Complex 2 isomerizes to 5 when refluxed in 1,2-dichloroethane. The crystal structures of 2 and 4 have been determined by X-ray diffraction studies.

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

Final Thoughts on Chemistry for Bis(dibenzylideneacetone)palladium

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Palladium-Catalyzed Allylation of Cyclopropyl Acetylenes with Oxindoles to Construct 1,3-Dienes

A novel palladium-catalyzed allylic alkylation of oxindoles with cyclopropyl acetylenes has been developed. Various 1,3-diene oxindole framework bearing a quaternary stereocenter at the C3 position were synthesized straightforwardly in good to excellent yields with high regio-, and stereoselectivities. The reaction exhibited high atom economy and good functional group tolerance.

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

A new application about Bis(dibenzylideneacetone)palladium

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An efficient class of bis-NHC salts: Applications in Pd-catalyzed reactions under mild reaction conditions

This study describes an efficient class of bis-N-heterocyclic carbene (bis-NHC) salts that can be easily made from commercially available and inexpensive starting materials. The application of these salts to Pd-catalyzed reactions is described. The palladium (Pd) catalyst generated in situ was highly effective under mild reaction conditions.

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

Awesome Chemistry Experiments For Bis(dibenzylideneacetone)palladium

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Palladium-assisted formation of carbon-carbon bonds. 9. Synthesis of (2-alkenylaryl)- and indenylpalladium complexes

(o-Formylaryl)palladium complexes [Pd{C6H(CHO)-6-R3-2,3,4}X(N-N)] [R = OMe; X = Cl; N-N = bpy (2,2?-bipyridine) (1a), tmeda (N,N,N?,N?-tetramethylethylenediamine) (1b). R = H; X = Br; N-N = bpy (2a), tmeda (2b)] react with ylides PhCHqqPPh3, pyCHqqPPh3 (py = 2-pyridyl), or ClCHqqPPh3 to give the (o-alkenylaryl)palladium derivatives [Pd{C6-HCHqqCHPh-6-(OMe)3-2,3,4}Cl(N-N)] [N-N = bpy (3a), N-N = tmeda (3b)], [Pd{C6HCHqqCHpy-6-(OMe)3-2,3,4}Cl(N-N)] [N-N = bpy (4)], [Pd{C6H(E-CHqqCHCl)-6-(OMe)3-2,3,4}-Cl(tmeda)] (5), or [Pd(C6H4CHqqCHPh-2)Br(N-N)] [N-N = bpy (6a), N-N = tmeda (6b)]. The compounds 3a, 4, and 6a,b are obtained as mixtures of E and Z isomers, whereas the formation of 3b and 5 is stereoselective (E isomer). The reaction of the (o-acetylaryl)palladium complexes [Pd{C6HC(O)Me-6-(OMe)3-2,3,4}Cl(tmeda)] (7) and [Pd{C6H4(C(O)Me)-2}Br(bpy)] (8) with bases results in the formation of the 3-palladaindan-1-ones [Pd(kappa2-{C6HC(O)CH2-6-(OMe)3-2, 3,4})(tmeda)] (9) and [Pd(kappa2-{C6H4C(O)CH2-2}(bpy)] (10). Complexes 3b and 6a,b react with alkynes RCqqCR? to give indenylpalladium complexes [Pd{eta-C9HBn-1-R-2-R?-3-(OMe)3-5, 6,7}(tmeda)]TfO [Bn = benzyl, TfO = CF3SO3, R = R? = Me (11); R = C(O)Me, R? = H (12)] and [Pd{eta-C9H4Bn-1-R-2-R?-3}(N-N)]TfO [R = R? = H, N-N = bpy (13a), tmeda (13b); R = R? = Me, N-N = bpy (14a), tmeda (14b); R = R? = Et, N-N = bpy (15a), tmeda (15b); R = R? = Ph, N-N = bpy (16a), tmeda (16b); R = Ph, R? = H and R = H, R? = Ph, N-N = bpy (17a); R = H, R? = Ph, N-N = tmeda (17b); R = Ph, R? = Me, N-N = bpy (18a), N-N = tmeda (18b)]. Complex 3b reacts with Me2CqqCqqCH2, CS2, or MeNqqCqqS to give [Pd(eta3-CMe2C{C6H(E-CHqqCHPh)- 6-(OMe)3-2,3,4}CH2)(tmeda)]TfO (19), [Pd(S2C{C6H-(E-CHqqCHPh)-6-(OMe)3-2,3,4}) (tmeda)]TfO (20), or [Pd(SC(NMe){C6H(E-CHqqCHPh)-6-(OMe)3-2,3,4}) (tmeda)]TfO (21). The crystal structures of 12, 17b, and 18a have been determined; the hapticities of the indenyl five-membered rings are intermediate between eta3 and eta5.

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