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In this report, we describe the generation of remote allylic quaternary stereocenters beta, gamma, and delta relative to a carbonyl in high enantioselectivity. We utilize a redox-relay Heck reaction between alkenyl triflates and acyclic trisubstituted alkenols of varying chain-lengths. A wide array of terminal (E)-alkenyl triflates are suitable for this process. The utility of this functionalization is validated further by conversion of the products, via simple organic processes to access remotely functionalized chiral tertiary acid, amine, and alcohol products.

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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 efficient methodology provides an easy access to highly optically active polysubstituted butenolides starting from aryl halides and 1:1:salts of optically active 2,3-allenoic acid-base via an oxidative addition-coordinative cyclization-reductive elimination mechanism, which led to the high efficiency of this chirality isomerization reaction.

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

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A palladium-catalyzed multicomponent synthetic route to polysubstituted pyrroles from aryl iodides, imines, carbon monoxide, and alkynes is described. To develop this reaction, a series of mechanistic studies on the [Pd(allyl)Cl]2/PtBu3 catalyzed synthesis of imidazolinium carboxylates from aryl iodides, imines, and carbon monoxide were first performed, including model reactions for each individual step in the transformation. These show that this reaction proceeds in a concurrent tandem catalytic fashion, and involves the in situ formation of acid chlorides, N-Acyl iminium salts, and ultimately 1,3-dipoles, i.e., Muenchnones, for subsequent cycloaddition. By employing a Pd(PtBu3)2/Bu4NCl catalyst, this information was used to design the first four-component synthesis of Muenchnones. Coupling the latter with 1,3-dipolar cycloaddition with electron deficient alkynes or alkenes can be used to generate diverse families of highly substituted pyrroles in good yield. This represents a modular and streamlined new approach to this class of heterocycles from readily accessible starting materials.

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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 carbonylation of 1-arylethanols was studied using homogeneous Pd complex catalysts in the presence of TsOH and LiCl as promoters. A combination of PdCl2(PPh3)2 as the catalyst and TsOH and LiCl at a 1:1 ratio gave considerably higher catalytic activity and > 95% 2-arylpropionic acid selectivity at 338 K and 5.4 MPa CO partial pressure. Concentration of promoters and water had a significant positive influence on catalytic activity and regioselectivity to Ibuprofen. However, at higher amounts of water, catalytic activity and selectivity decreased considerably due to the change of homogeneous nature of the system to biphasic. The Pd(0) species formed after the reduction of the Pd(II) precursor exists mostly as anionic species ligated with Cl- ions. A catalytic cycle initiated by the oxidative addition of IBPCl to anionic Pd(0) species, e.g., Pd(PPh3)2Cl- or Pd(CO)(PPh3)2Cl- was proposed.

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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 synthesis of a series of gem- and vic-diborylated vinylsilanes was accomplished via highly selective transition-metal-catalyzed syn-dimetalation to the alkynylmetal species. This protocol served as a general synthetic method toward regio- and stereodefined multisubstituted olefins. The key steps are the diastereoselective Suzuki-Miyaura cross-coupling reactions of gem- and vic-diborylated vinylsilanes, in which the two boron groups showed discrete reactivities to afford diverse precursors of multisubstituted olefins.

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

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In homogeneous catalysis, the catalyst is in the same phase as the reactant. The number of collisions between reactants and catalyst is at a maximum.In a patent, 52522-40-4, name is Tris(dibenzylideneacetone)dipalladium-chloroform, introducing its new discovery. COA of Formula: C52H43Cl3O3Pd2

The novel P,N-ligand 2-[2-(diphenylphosphino)phenyl]-4,5-dihydro-4-methyl-4-phenyloxazole (2a) has been synthesized. The corresponding [PdII(eta3-diphenylallyl) (2a)]PF6 (3a) and [PdII(eta3-1,3-dimethylallyl) (2a)]PF6 (4a) complexes have been studied by X-ray analysis and NMR spectroscopy. 3a exists as exo-syn-syn isomer in the solid state. In solution, the same isomer predominates. The X-ray structure of 4a reveals that the oxazoline ligand is coordinated in a pseudo-enantiomeric conformation compared with 3a. A syn-anti arrangement of the allyl substituents is favored in the solid state. NMR spectroscopical investigations suggest a formation of six isomers in solution due to endo-exo orientation of the allyl moiety and syn-anti isomerization of the methyl substituents. NMR data of [Pd0(eta2-dimethylfumarate)(phosphinooxazoline)] complexes give evidence that two isomers exist in solution. The isomeric ratio is strongly dependent on the steric bulk of the oxazoline substituents. The solid state structures of [Pd0(eta2-dmfu) (2c)] and [Pd0(eta2-dmfu) (1a)] confirmed the structures of the main isomer found in solution. The asymmetric allylic substitution reaction of 1,3-diphenylallyl acetate with dimethyl malonate catalyzed by 3a proceeds with a selectivity of 97% ee. The ee induced by 2a in catalytic allylic substitution of 1-methylbutenyl acetate is moderate (18%). A comparison of the intermediate 4a and 5a as model of the actual olefinic intermediate suggests that the poor enantioselectivity achieved with ligand 2a is due to the preferred formation of anti-isomers of the allylic intermediate 4a and the conformational instability of the complex.

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

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A tandem relay catalytic protocol using both Pd and isothiourea catalysis has been developed for the enantioselective synthesis of alpha-amino acid derivatives containing two stereogenic centers from readily accessible N,N-disubstituted glycine aryl esters and allylic phosphates. The optimized process uses a bench-stable succinimide-based Pd precatalyst (FurCat) to promote Pd-catalyzed allylic ammonium salt generation from the allylic phosphate and the glycine aryl ester. Subsequent in situ enantioselective [2,3]-sigmatropic rearrangement catalyzed by the isothiourea benzotetramisole forms syn-alpha-amino acid derivatives with high diastereo- and enantioselectivity. This methodology is most effective using 4-nitrophenylglycine esters and tolerates a variety of substituted cinnamic and styrenyl allylic ethyl phosphates. The use of challenging unsymmetrical N-allyl-N-methylglycine esters is also tolerated under the catalytic relay conditions without compromising stereoselectivity.

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

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Tandem Pd-catalyzed C-C coupling/recyclization of 2-(2-bromoaryl)cyclopropane-1,1-dicarboxylates with primary nitro alkanes

The first successful synthesis of 1H-2,3-benzoxazine 3-oxides has been described. The efficiency of the approach is provided by the C-C-coupling of 2-(2-bromoaryl)cyclopropane-1,1-dicarboxylates with primary nitroalkanes catalyzed by Pd(dba)2/JohnPhos system followed by in situ recyclization of the intermediates. Several representative transformations allowing selective modification of the nitronate as well as malonate functionalities in the resulting compounds are demonstrated.

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

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Structural characterization of the head-to-head isomers of the [Pd2(Ph2Ppy)2Cl2] and [PtPd(Ph2Ppy)2I2] complexes (Ph2Ppy = 2-(diphenylphosphino)pyridine)

The molecular structures of the thermodynamically unstable head-to-head isomers, HH-[Pd2(Ph2Ppy)2Cl2] and HH-[PtPd(Ph2Ppy)2I2], have been determined by single crystal X-ray diffraction. The two complexes have proved to be isostructural. The severe distortions of the bond angles from the ideal square planar geometry around the metal centers ligating the trans phosphorus donor atoms are indicative of a more pronounced internal strain in the HH isomers as compared to the HT counterparts. The enhanced internal strain is thought to be the major driving force responsible for the spontaneous conversion of the head-to-head isomers to their head-to-tail congeners. 13C NMR spectra in solution phase as well as solid-state 31P MAS NMR spectra have proved to be informative regarding the orientation of the asymmetric Ph2Ppy ligands.

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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 role of ancillary ligands and of electron poor alkenes and alkynes in stabilizing Pd(0) derivatives: A comparative study

The peculiar characteristics of the ligand neocuproine (2,9-dimethylphenanthroline) allow a number of exchange equilibrium studies between the low valence complex [Pd(eta2-nq)(Neocup)] (nq = naphthoquinone; Neocup = neocuproine) and several alkenes and alkynes. A new order of stability which compares differently unsaturated molecules was established. An overview of the factors governing the stability of palladium(0) alkene and alkyne derivatives as a function of the steric and electronic characteristics of both the unsaturated molecule and the ligand becomes accessible and a comparison with the previously determined order was therefore feasible. Such a comparison enlightens the importance of the substituent methyl groups in ortho position of the hetero-aromatic ring which represents the molecular fragment common to all the ligands considered. Taking advantage of the steric requirements of the alkene tmetc (tmetc = tetramethylethylenetetracarboxylate) a kinetic investigation of the reaction between the olefin itself and the complexes [Pd(eta2-dmfu)(L-L?)] (dmfu = dimethylfumarate; L-L? = 8-diphenylphosphanyl-2-methyl-quinoline, neocuproine, phenanthroline) was carried out. The structures of the complexes [Pd(eta2-dmfu)(DPPQ)] and [Pd(eta2-deta)(Neocup)] (deta = but-2-ynedioc acid diethyl ester) were also reported in the present paper. The structure of the latter represents the first example of a palladium(0) complex in which the N2C2 donor set around the metal centre is supported by a chelating eta2-alkyne.

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