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Making advances: Efficient strategies relying on palladium-catalyzed cross-coupling reactions are now available for the assembly of tri- and tetrasubstituted alkenes with excellent stereocontrol (see scheme; Y = Hal, X = ZnHal or MgHal; other variants: Y = BR2, X = I). (Chemical Equation Presented).

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

Brief introduction of Bis(dibenzylideneacetone)palladium

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A study has been made of the reductive carbonylation of 2,4-dinitrotoluene (2,4-DNT) to 2,4-diisocyanotoluene (2,4-TDI) with catalysis either by , in the presence of FeO3 and MoO3 or of Fe(MoO4)3 as cocatalysts, or by Pd0 complexes without cocatalysts.In the case of catalytic systems based upon the reaction can be carried out at about 200 deg C and under 200 atm of CO to produce 2,4-TDI with high conversions and acceptable selectivities.With Pd0 complexes as catalysts good conversions can be achieved at much lower temperatures (100-120 deg C) but with a low selectivity when a higher pressure of CO is used (300 atm or more).An investigation of the reductive cabonylation of nitrobenzene to phenylisocyanate as a model system, together with a study of the thermal stability of in the presence of CO, has provided evidence that the actual active catalyst could be a reduced (probably zerovalent) form of palladium stabilised by the nitroaromatic substrate or by some of the products formed from it as ligands.

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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 Pd2(DBA)3

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This review summarizes the state of knowledge on the chemical methods of C(5)-modifications of uridine and cytidine derivatives and may serve as a useful tool for synthetic chemists to choose an appropriate reaction protocol. The synthesis of 5-substituted uracil derivatives is gaining an increasing interest because of their possible applications in medicine and pharmacy. Modifications at the C(5) position of pyrimidine nucleosides can enhance their biostability, bioavailability or(and) biological activity. Among the C(5)-modified nucleosides, 5-halopyrimidines exhibit anticancer, antiviral, radio- and photosensitizing properties. Besides 5-halo-substituted derivatives, there are other examples of nucleosides with confirmed biological activity containing a C-C bond at the C(5) position in the pyrimidine ring. In recent decades, scientists have achieved great progress in the field of cross-coupling reactions. Among them, nickel-catalyzed processes provide a broad spectrum of synthetic methods that are based on less toxic and cheaper starting materials. This review summarizes the synthetic approaches based on the coupling or halogenation reactions, which enable 5-substituted pyrimidine nucleosides to be obtained. Moreover, the importance of the systems considered for medicine and pharmacy is briefly discussed. The bibliography includes 197 references.

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

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Palladium-catalyzed decarboxylative alkynylation of alpha-acyloxyketones triggered by C(sp3)?O bond cleavage is disclosed. The decarboxylation strategy featuring a neutral reaction condition enabled an unprecedent catalytic alkynylation of a ketone enolate. The reaction was applied to a variety of substrates, giving desired products in good yields. We successfully obtained X-ray crystallography of a new palladium?enolate intermediate that was synthesized by a reaction of [Pd(cod)(CH2TMS)2] with XPhos and alpha-acyloxyketone at room temperature, indicating facile C(sp3)?O bond disconnection.

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

Final Thoughts on Chemistry for (2,2′-Bipyridine)dichloropalladium(II)

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1p;&-5q; 1 The reactions of [Tl2{S2C=C{C(O)Me}2}]n with [MCl2L2] (1:1) or with [MCl2(NCPh)2] and PPh3 (1:1:2) give complexes [M{eta2-S2C=C{C(O)Me}2}L2] [M = Pt, L2 = 1,5-cyclooctadiene (cod) (1); L2 = bpy, M = Pd (2a), Pt (2b), L = PPh3, M = Pd (3a), Pt (3b)] whereas with MCl2 and QCl (2:1:2) anionic derivatives Q2[M{eta2-S2C=C{C(O)Me}2}2] [M = Pd, Q = NMe4 (4a), Ph3P=N=PPh3 (PPN) (4a?), M = Pt, Q = NMe4 (4b)] are produced. Complexes 1 and 3 react with AgClO4 (1:1) to give tetranuclear complexes [{ML2}2Ag2-{mu2, eta2-(S,S?)-{S2C=C{C (O)Me}2}2}](ClO4)2 [L = PPh3, M = Pd (5a), Pt (5b), L2 = cod, M = Pt (5b?)], while the reactions of 3 with AgClO4 and PPh3 (1:1:2) give dinuclear [{M(PPh3)2}{Ag(PPh3)2} {mu2,eta2-(S,S?) -{S2C=C{C(O)Me}2}}]ClO4 [M = Pd (6a), Pt (6b)]. The crystal structures of 3a, 3b, 4a, and two crystal forms of 5b have been determined. The two crystal forms of 5b display two {Pt(PPh3)2}{mu2,eta2- (S,S?)-{S2C=C{C(O)Me}2}2} moieties bridging two Ag(I) centers.

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

Discovery of Pd2(DBA)3

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Stereoselective construction of various O-glycosidic bonds was first achieved by different palladium sources using 3,4-O-carbonate galactal as the donor to reach yields up to 95% under mild conditions. With Pd(II) catalyst coordination of this glycal donor from the beta-face directed by carbonate group, hard nucleophiles (aliphatic alcohols) gave beta-glycosides and alpha-glycosides were obtained from soft nucleophiles (phenols). In contrast, with the Pd(0) catalyst coordinating the donor from the beta-face due to steric effect, both hard and soft acceptors could only generate beta-glycosides via hydrogen-bond-mediated aglycone delivery.

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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 cycloaddition of alkynylboronates and sydnones provides a convenientand highly regioselective method for the synthesis of a broad range of di-, tri-, and tetrasubstituted pyrazole boronic esters. The origins of an observed regiochemical divergence in the reactions of terminal alkyny lboronates with their more substituted analogues have been studied by DFT methods.

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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 active, general, and long-lived palladium catalyst for Suzuki-Miyaura reactions of aryl and heteroaryl chlorides deactivated by steric hindrance, electron richness, and coordinating functional groups is reported. In reactions of arylbromide bearing two o-tert-butyl substituents, C(sp3)-H arylation of the tert-butyl group, rather than the Suzuki-Miyaura reaction, proceeded in excellent yield. The key to the success of the reactions was the development of biphenylene-substituted dicyclohexylruthenocenylphosphine (CyR-Phos) as a supporting ligand.

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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 unprecedented remote amide-directed palladium-catalyzed intermolecular highly selective benzylic C-H amination with N-fluorobenzenesulfonimide is developed, which represents the first direct benzylic C-H amination with a non-nitrene nitrogen source. This methodology provides a novel approach to circumvent the common ortho aromatic C-H selectivity in directed palladium catalyzed C-H functionalization.

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

Discovery of Pd2(DBA)3

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Several Hiyama cross-coupling reactions of oxasilacycloalkenes and aryl iodides are described that produce trisubstituted Z-styrenes in moderate to excellent yields. Both electron-rich and electron-poor aryl iodides are tolerated in the cross-coupling reaction. The oxasilacycloalkene coupling partners were prepared by ruthenium-catalyzed intramolecular anti-hydrosilylation of alkynols. One of the cross-coupling products was converted to a 1-benzoxocane, albeit in low yield, using an intramolecular Buchwald-Hartwig etherification. The cyclic ether produced contains the carbon skeleton of heliannuol A.

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