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Palladium allyl, cinnamyl, and indenyl complexes with the ylide-substituted phosphines Cy3P+?C?(R)PCy2 (with R=Me (L1) or Ph (L2)) and Cy3P+?C?(Me)PtBu2 (L3) were prepared and applied as defined precatalysts in C?N coupling reactions. The complexes are highly active in the amination of 4-chlorotoluene with a series of different amines. Higher yields were observed with the precatalysts in comparison to the in situ generated catalysts. Changes in the ligand structures allowed for improved selectivities by shutting down beta-hydride elimination or diarylation reactions. Particularly, the complexes based on L2 (joYPhos) revealed to be universal precatalysts for various amines and aryl halides. Full conversions to the desired products are reached mostly within 1 h reaction time at room temperature, thus making L2 to one of the most efficient ligands in C?N coupling reactions. The applicability of the catalysts was demonstrated for aryl chlorides, bromides and iodides together with primary and secondary aryl and alkyl amines, including gram-scale applications also with low catalyst loadings of down to 0.05 mol %. Kinetic studies further demonstrated the outstanding activity of the precatalysts with TOF over 10.000 h?1.

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

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Subtle modulation of the electronic properties of the dibenzylideneacetone (dba) ligand allows the development of an efficient protocol for the Heck alkenylation of 5-iodo-2?-deoxyuridine. This protocol enables the large-scale synthesis of commercially important nucleoside building blocks. The isolation of one key molecule was accomplished under column-free conditions on a 10-gram scale.

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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 general and highly enantioselective arylation of carbamates derived from primary alcohols was developed by combining Hoppe’s sparteine-mediated asymmetric lithiation with Negishi cross-coupling. Coupled with Aggarwal’s lithiation-borylation sequence, the current method provides a short and divergent access to a variety of enantioenriched secondary and tertiary benzylic alcohols.

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

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Three benzenedicarboxamide ligands (L) were designed and synthesized, and each was used to prepare a palladium(II) complex Pd(L)Br and Pd(L)(OAc). These NCN pincer complexes were used to catalyze the alpha-arylations of a variety of ketones with aryl chlorides or bromides in various solvents, and moderate-to-excellent yields were obtained (up to 95%). Further research showed that unactivated and sterically hindered aryl halides and ketones are also suitable substrates for the synthesis of alpha-arylation. Graphical Abstract: [Figure not available: see fulltext.].

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

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Dithienosilole-benzothiadiazole based low bandgap copolymers remain promising material for organic photovoltaics. A new copolymer, poly[(4,4?-dioctyldithieno[3,2-b:2?,3?-d]silole-2,6-diyl) -alt-{4,7-bis[2-(3-hexyl)thienyl]-2,1,3-benzothiadiazole-5,5?-diyl}] (PDTSDTBT) was designed by introducing a thiophene spacer bearing a hexyl chain at beta-position in the main backbone and compared to its analog poly[(4,4?-dioctyldithieno[3,2-b:2?,3?-d]silole-2,6-diyl) -alt-(2,1,3-benzothiadiazole-4,7-diyl)] (PDTSBT). In PDTSDTBT, linear alkyl chains on silicon were chosen due to facile and cheap access and the inserted 3-hexylthiophene units were chosen to increase solubility and molar mass, a weak point with PDTSBT. The two parameters are important to optimize photovoltaic performances. To compare characteristics, PDTSDTBT of molar masses greater than, and equal to a sample of PDTSBT, were prepared. Pd-catalyzed Stille cross-coupling reactions in a micro-wave reactor to promote an efficient copolymerisations. A strong absorption ranging from 370 nm to 800 nm and a good thermal stability were observed. PDTSDTBT showed better solubility and higher degree of crystallinity. Facile synthesis of high molar masses meant that higher efficiencies, around 40% greater, could be obtained with PDTSDTBT. The polymer was demonstrated to be susceptible to improvement through the use of device-additives. For example, under initial optimisations using PDTSDTBT:PC60BM blend at a ratio of 1:1 delivered a power conversion efficiency of 2.13% with JSC = 7.73 (mA/cm2), under AM 1.5 (100 mW/cm2) illumination.

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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 Pd(0)-catalyzed cyclization-allylation reactions of 2-alkynylbenzamides proceed with high regioselectivity to afford the 6-endo-cyclization-derived products 4-allyl-isochromen-1-imines. DFT calculations have been performed on this and the related arylation reaction, that has been reported to afford the products corresponding to an exo-cyclization under similarly Pd(0)-catalyzed conditions. Under the reaction conditions, these cyclizations are presumed to be triggered by activation of the C-C triple bond with either an allyl- or an aryl palladium complex, generated by oxidative addition of an allyl- or aryl halide to the Pd(0) catalyst. For reactions promoted by allylpalladium species, calculations predict a reversible cyclization, followed by a regioselectivity-determining endo-selective reductive elimination. In contrast, according to calculations, the corresponding arylations would proceed through irreversible exo-selective cyclization and reductive elimination steps. These predictions are consistent with the experimental observations. The divergent regiochemical outcome appears to have its origin in the differences caused on the intermediate palladium complexes by the groups derived from the coupling agents (allyl or aryl) and by the reaction conditions (solvent and ligands) through a subtle interplay of polarity and coordinative effects.

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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 direct synthesis of new hemilabile ligands from the economical, readily available lactone phthalide is described. Pd-complexes of one such ligand were found highly effective in general Suzuki-Miyaura cross-coupling reactions, including deactivated and hindered aryl chlorides. The Royal Society of Chemistry 2013.

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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 new photoredox-catalyzed chlorotrifluoromethylation reaction of internal arylalkynes under mild conditions using visible light has been developed. The reactions proceed with high levels of regio- and stereoselectivity and utilize commercially available CF3SO2Cl as both the CF3 and Cl source. In the mechanistic pathway for this process, generation of the CF3 radical and chloride ion occurs by Ir(ppy)3-photocatalyzed reductive decomposition of CF3SO2Cl. The synthetically important trifluoromethyl-substituted vinyl chlorides produced in this process can be readily transformed to 1,1-bis-arylalkenes by using Suzuki coupling.

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

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trans-Arylvinylboronate derivatives are important synthesis blocks in natural products, pharmaceuticals and organic materials. There are only a few reaction conditions that could selectively provide trans-arylvinylboronates by Heck coupling of pinacol vinylboronate and aryl halides. Here we report an efficient and versatile method of palladium catalyzed cross-coupling between pinacol vinylboronate and various aryl or hetaryl bromides to obtain the corresponding trans-(het)arylvinylboronates in excellent yields and selectivity. 30 examples have been synthesized using this protocol which offers an alternative method to prepare these useful building blocks.

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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 new strategy was developed for intercepting the palladium-alkyl species generated in Heck reaction via nucleophilic addition prior to the step of migratory insertion, which leads to a new palladium-catalyzed difunctionalization of enol ethers with aminals and alcohols to afford amino acetals. Mechanistic studies suggested that the cationic cyclometalated Pd(II) complex generated by the oxidative addition of aminal to a Pd(0) species was crucial for this unusual transformation.

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