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Esters are chemical compounds with many practical uses. The common type of esterification is called the Fischer esterification. Another one is by the action of acid chlorides on alcohols but not with tertiary alcohols. The stable carbenium ions formed from tertiary alcohols favor elimination and the byproduct, hydrogen chloride prevents ester formation. In this new report, palladium inserted ArCOPdCl species reacts with tertiary alcohols and cross-coupling under microwave heating, minimizes the formation of probable carbenium ion, and promotes successful production of highly substituted esters in good to high 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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A highly efficient protocol for the synthesis of diverse aryl (heteroaryl) substituted pyridyl oxadiazol-2(3H)-one analogues using Suzuki-Miyaura cross-coupling strategy under microwave enhanced conditions is developed. The method is found to be compatible with a wide range of aryl (heteroaryl) boronic acids.

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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 palladium-catalyzed borylation of aryl iodides with 2,3-dihydro-1H-benzo[d][1,3,2]diazaboroles was achieved. The mild reaction conditions employed allowed for the inclusion of a wide variety of functional groups in aryl iodides to be tolerated. Additionally, the borylated products can be transformed into the corresponding boronic acids or their esters under acidic 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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A protected pyruvate equivalent is described that allows arylation and arylation/alkylation reactions to be performed at the methyl group. Utilization of the OBO derivative of the pyruvate ester allowed the application of palladium catalyzed arylation reactions together with subsequent alkylation, under basic conditions. Moreover, the OBO protecting group could be easily removed in one step to provide access to a wide range of substituted pyruvate derivatives.

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

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Well-defined, air-stable Pd complexes of bis-phosphinoferrocene family of catalysts have been studied in the arylation of various ketones with aryl chlorides and aryl bromides. Bis(di-tert-butyl)phosphinoferrocene (DtBPF)-based catalysts such as (DtBPF) PdCl2 and (DtBPF)PdBr2 have been identified as two of the most active catalysts for the alpha-arylation of a model reaction involving propiophenone and 4-chlorotoluene. The scope of the (DtBPF)-PdCl2 catalyst has been efficiently expanded to the arylation of various ketones with aryl chlorides and bromides with up to 97% isolated yields, under relatively mild reaction conditions at low catalyst loadings. The efficacy of the (DtBPF)PdCl2 catalyst was demonstrated at very low catalyst loadings with S/C 10,000 for the difficult aryl bromide, 4-bromoanisole, and 2000 for the electron-neutral aryl chloride, 4-chlorotoluene, on ~10-g scale with excellent isolated yields and lower Pd in the product (6 and 48 ppm, respectively). Comparative studies on the Pd:DtBPF molar ratios between in situ catalysts and preisolated catalysts revealed that preisolated (DtBPF)PdX2 (X = CI, Br) are the catalysts of choice due to various practical reasons.

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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 reaction of [Pd(dtbpf)Cl2] (dtbpf = 1,1?-bis(di-tert-butylphosphino)ferrocene) with sodium bromide yields [Pd(dtbpf)Br][Br], which displays an interaction between the iron and palladium atoms. The structure of this compound has been obtained and is compared to those of the previously reported [Pd(dtbpf)X]+ (X = Cl, I) analogues. Similar to [Pd(dtbpf)Cl]+, [Pd(dtbpf)Br]+ appears to undergo a solid-state isomerization at low temperature to a species in which the Fe-Pd interaction is disrupted. In addition to 1H and 31P{1H} NMR and visible spectroscopy, the [Pd(dtbpf)X]+ (X = Cl, Br) compounds were also characterized by zero-field 57Fe Moessbauer spectroscopy. DFT calculations on [Pd(dtbpf)X]+ (X = Cl, Br, I) show that the Fe-Pd interaction is weak and noncovalent and that the strength of the interaction decreases as the halide becomes larger. A related trend is noted in the potential at which oxidation of the iron center occurs; the larger the halide, the less positive the potential at which oxidation occurs. Finally, the catalytic activity of [Pd(dtbpf)X]+ (X = Cl, Br, I) in the arylation of an aromatic ketone was examined and compared to the activity of [Pd(dtbpf)Cl2].

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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 and scalable synthesis of AZD3264 is described in which the differential reactivities of various halogen atoms have been employed. The process involves five linear chemical steps with three isolated stages starting from commercially available fragments.

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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 invention relates to provide a following formula (III) shown imidazole fused ring compound synthesis method, the method comprising: in the organic solvent, the catalyst, organic ligand, assistant and the presence of a base, the following formula (I) compounds of the following formula (II) compound and the reaction, thereby obtaining states the type (III) compound, Wherein R1 Is selected from H, C1 – C6 Alkyl or halogen; R2 Is selected from H, C1 – C6 Alkyl, C1 – C6 Alkoxy or halogen; R3 , R4 Are each independently selected from H, C1 – C6 Alkyl, C1 – C6 Alkoxy or halogen; X is halogen. The method through the catalyst, organic ligand, compounding chemicals, alkali and organic solvent in coordination with the comprehensive selective, thus can yield to obtain the target product, in the technical field of pharmaceutical intermediate synthesis has good application prospect and a wide range of industrial production potential. (by machine translation)

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

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Multi-drug resistant tuberculosis (MDR-TB) is of growing global concern and threatens to undermine increasing efforts to control the worldwide spread of tuberculosis (TB). Bedaquiline has recently emerged as a new drug developed to specifically treat MDR-TB. Despite being highly effective as a result of its unique mode of action, bedaquiline has been associated with significant toxicities and as such, safety concerns are limiting its clinical use. In order to access pharmaceutical agents that exhibit an improved safety profile for the treatment of MDR-TB, new synthetic pathways to facilitate the preparation of bedaquiline and analogues thereof have been discovered.

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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 specification relates to compounds of Formula (I) and pharmaceutically acceptable salts thereof. The specification also relates to processes and intermediates used for their preparation, pharmaceutical compositions containing them and their use in the treatment of cell proliferative disorders.

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