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A palladium-catalyzed coupling reaction of 2,3-allenylic carbonates with cyclopropanols was developed, affording valuable 1,3-diene products with different functional groups efficiently under mild reaction conditions. Gram scale synthesis was easily conducted with synthetic transformations 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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(Triethylgermyl)tributylstannane reacts metal-selectively with allylic halides at room temperature (r.t.) in the presence of tris(dibenzylideneacetone)dipalladium, Pd2(dba)3CHCl3, to provide an alternative route to allylgermanes. (Dimethylphenylgermyl)tributylstannane regio- and stereoselectively reacts more readily with allylic halides than (triethylgermyl)tributylstannane affording the corresponding allylgermanes in quantitative yields.

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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 metalation of 4,4-dimethyloxazoline using TMPZnCl·LiCl provides a stable 2-zincated oxazolinyl reagent which readily undergoes palladium-catalyzed Negishi cross-couplings allowing a new access to 2-aryloxazolines. Cu-mediated acylation and allylation reactions also proceed in good yields. This journal is

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

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In heterogeneous catalysis, the catalyst is in a different phase from the reactants. Formula: C34H28O2Pd, 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

Lithium 2,2,6,6-tetramethylpiperidide (LTMP)-induced intramolecular cyclopropanation of unsaturated terminal epoxides provides an efficient and completely stereoselective entry to bicyclo[3.1.0]hexan-2-ols and bicyclo[4.1.0]heptan-2-ols. Further elaboration of C-5 and C-6 stannyl-substituted bicyclo[3.1.0]-hexan-2-ols via Sn-Li exchange/electrophile trapping or Stille coupling generates a range of substituted bicyclic cyclopropanes. An alternative straightforward cyclopropanation protocol using a catalytic amount of 2,2,6,6-tetramethylpiperidine (TMP) allows for a convenient (1 g-7.5 kg) synthesis of bicyclo[3.1.0]-hexan-2-ol and other bicyclic adducts. The synthetic utility of this chemistry has been demonstrated in a concise asymmetric synthesis of (+)-beta-cuparenone. The related unsaturated chlorohydrins also undergo intramolecular cyclopropanation via in situ epoxide formation.

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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 sodium salts of allyldimethylsilanol and 2-butenyldimethylsilanol undergo palladium-catalyzed cross-coupling with a wide variety of aryl bromides to afford allylated and crotylated arenes. The coupling of both silanolates required extensive optimization to deliver the expected products in high yields. The reaction of the allyldimethylsilanolate takes place at 85C in 1,2-dimethoxyethane with allylpalladium chloride dimer (2.5 mol %) to afford 73-95% yields of the allylation products. Both electron-rich and sterically hindered bromides reacted smoothly, whereas electron-poor bromides cross-coupled in poor yield because of a secondary isomerization to the 1-propenyl isomer (and subsequent polymerization). The 2-butenyldimethylsilanolate (E/Z, 80:20) required additional optimization to maximize the formation of the branched (gamma-substitution) product. A remarkable influence of added alkenes (dibenzylideneacetone and norbornadiene) led to good selectivities for electron-rich and electron-poor bromides in 40-83% yields. However, bromides containing coordinating groups (particularly in the ortho position) gave lower, and in one case even reversed, selectivity. Configurationally homogeneous (E)-silanolates gave slightly higher gamma-selectivity than the pure (Z)-silanolates. A unified mechanistic picture involving initial gamma-transmetalation followed by direct reductive elimination or sigma-pi isomerization can rationalize all of the observed trends.

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

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Cascade Pd-catalyzed alkene carboamination/Diels-Alder reactions between bromodienes and amines bearing two pendant alkenes are described. These transformations generate 4 bonds, 3 rings, and 3-5 stereocenters to afford polycyclic nitrogen heterocycles with high diastereoselectivity. (Chemical Equation 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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Phosphorus-sulfur-containing hybrid calixphyrins were prepared by the BF3-promoted dehydrative condensation between sigma4-2,5-bis[(pyrrol-2-yl)methyl]phosphole and 2,5-bis[hydroxy(phenyl)methyl]thiophene. X-ray crystallographic analysis of the Pd-P,N2,S-hybrid calixphyrin complex revealed that the Pd center was coordinated by the four heteroatoms to adopt a distorted square planar geometry. The Pd complex, displaying a characteristic reddish purple color in solution, catalyzed the Heck reaction of bromoarenes with n-butyl acrylate with high efficiency at elevated temperatures. Copyright

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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 efficient C-H acylation reaction of biaryl-2-amines and aromatic aldehydes is developed. This dehydrogenative cross-coupling protocol could furnish monoacylation and diacylation products in moderate to good yields with a broad substrate scope and good regioselectivity.

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

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This paper describes the synthesis of a series of PdIV complexes containing modular monoanionic tridentate facially coordinated NNN and NNC donor ligands. In all cases, these complexes are stable to reductive elimination for a minimum of several days in solution at room temperature. With appropriately designed tridentate ligands, the PdIV adducts participate in both ligand substitution and C-H activation reactions. Overall, this work shows that unsymmetrical fac-L2X type ligands can serve as versatile and tunable scaffolds for modulating the reactivity of octahedral PdIV complexes.

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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 mechanism, which is distinct from the traditional one when sodium alkoxide was used instead of tertiary amines, was proposed for the alkoxycarbonylation of aryl iodides. The catalytic cycle was composed of oxidative addition, subsequent ArPdOR formation, CO insertion to Pd-OR, and final reductive elimination of ArPdCOOR. The kinetic simultaneity of the formation of deiodinated side product from the aryl iodide and aldehyde from corresponding alcohol provided strong evidence for the existence of ArPdOR species. The observation of thioether, as the other competitive product in palladium catalyzed thiocarbonylation of aryl iodides and sodium alkylthiolate, also indicate the possibility of metathesis between ArPdl and sodium alkylthiolate. Preliminary kinetic studies revealed that neither oxidative addition nor reductive elimination was rate limiting. DFT calculation displayed preference for CO insertion into Pd-OR bond. The advantage of this novel mechanism had been demonstrated in the facile alkoxycarbonylation and thiocarbonylation. The ethoxycarbonylation of aryl iodides under room temperature and balloon pressure of CO in the presence of EtONa were examined, and good to high yields were obtained; the t-butoxycarbonylation reactions in the presence of t-BuONa were achieved, and the alkylthiocarbonylation (including the t-butylthiocarbonylation) of aryl iodides in the presence of sodium alkylthiolate were also investigated.

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