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A general synthetic scheme for tamoxifen-type tetrasubstituted olefins based on the novel Cu-catalyzed carbomagnesation across alkynyl(2-pyridyl)silane has been developed. A wide array of electronically and structurally diverse tetrasubstituted olefins can be prepared in a regiocontrolled, stereocontrolled, and diversity-oriented manner. Noteworthy features are that (i) the three aryl groups, which are believed to be important (essential) for anti-estrogenic activity, can be varied at will because they all stem from readily available aryl iodides, and (ii) any stereo- and regioisomers can, in principle, be prepared by simply changing the applying order of aryl iodides into the sequence. 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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The bis(tri-tert-butylphosphine)palladium(0) [Pd(tBu3P)2]-catalyzed synthesis of fluorinated closo-carboranes from 3D aromatic iodo-closo-carboranes by nucleophilic halogen exchange using silver(I) fluoride is described. Fluorination of 2-iodo-closo-p-carborane proceeded more readily than that of 9-iodo-closo-m-carborane. Iodine?fluorine exchange at 9-iodo-closo-o-carborane was not successful yielding instead a charge-compensated dibutylphosphonio nido-o-carborane. The described methodology advances the understanding of nucleophilic fluorination at aromatic systems by Pd0/PdII catalysis. With further optimization, it could find application in the synthesis of 18F-labeled carboranyl diagnostics for biomedical applications.

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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 series of shape-persistent macrocycles featuring both m-phenylene and 2,5-thiophene linkers has been synthesized, including an example where they bridge electron-rich (veratrole) and electron-poor (phthalimide) units. Charge transfer in this “push-pull macrocycle” has been investigated by UV-vis and fluorescence spectroscopies and DFT calculations. The effect of pairing structurally distinct conjugated bridges is discussed in the context of acyclic and symmetrical macrocyclic analogs.

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

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Traditional materials for application in organic light emitting diodes (OLEDs) are primarily based on small molecules and polymers, with much fewer examples of intermediate molecular weights materials. Our interest lies in this intermediate molecular weight range, specifically in hybrids based on 3-dimensional silsesquioxane (SSQ) cores that represents a new class of versatile materials for application in solution processable OLEDs. We report here SSQ based hybrids (P8-OVS and P14-OVS) that are easily prepared in one high-yield step from the Heck coupling of commercially available 1-bromopyrene with octavinyl-SSQ. The resulting materials offer numerous advantages for OLEDs including amorphous properties, high-glass-transition temperatures (Tg), low polydispersity, solubility in common solvents, and high purity via column chromatography. Solution processed OLEDs prepared from P8-OVS provide blue-green emission with external quantum efficiencies, current efficiencies, maximum brightness, and turn-on voltages of 2.63%, 8.28 cd/A, 36183 cd/m2, and 3.1 V, respectively. 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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Ni(cod)2/PtBu3 system catalyzed the dimerization of terminal alkynes to give (E)-head-to-head dimerization products, in which the stannylacetylene dimer could be applied to a one-pot synthesis of a conjugated enyne, when combined with Migita-Stille 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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This manuscript investigates the possibilities to obtain helical conjugated polymers following a controlled chain-growth polymerization mechanism with external initiation. Attempts to prepare poly(3,6-(9,10-di(octyloxy)) phenanthrene)s with the existing chain-growth mechanisms using existing Kumada or Negishi couplings were unsuccessful because of the difficulty to quantitatively prepare the Grignard metathesis reagent starting from the envisaged precursor, namely 3,6-dibromo-(9,10-di(octyloxy))phenanthrene. On the other hand, a Suzuki-Miyaura coupling polymerization using Pd(P tBu3) as the catalyst clearly allows the polymerization to proceed. The reaction conditions were optimized and an in-depth study with gel permeation chromatography and matrix-assisted laser desorption ionization time-of-flight (MALDI-ToF) of the underlying mechanisms was performed. Nevertheless, a prolonged chain-growth mechanism was not achieved for the targeted polymers. 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 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 alkali-metal salts (potassium and sodium) of a large number of aryl- and heteroarylsilanols undergo efficient cross-coupling with a wide range of aromatic bromides and chlorides under mild conditions to form polysubstituted biaryls. The critical feature for the success of these coupling reactions and their considerable scope is the use of bis(tri-tert-butylphosphine)palladium. Under the optimized conditions, electron-rich, electron-poor, and sterically hindered arylsilanolates afford cross-coupling products in good yields. Many functional groups are compatible with the coupling conditions such as esters, ketones, acetals, ethers, silyl ethers, and dimethylamino groups. Two particularly challenging substrates, (2-benzofuranyl)dimethylsilanolate and (2,6-dichlorophenyl)dimethylsilanolate prepared as their sodium salts showed excellent activity in the coupling reactions, in the former case also with aromatic chlorides. General methods for the efficient synthesis of a wide range of aromatic silanols are also described.

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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 series of monomeric arylpalladium(II) complexes LPd(Ph)X (L = 1-AdP tBu2, PtBu3, or Ph 5FcPtBu2 (Q-phos); X = Br, I, OTf) containing a single phosphine ligand have been prepared. Oxidative addition of aryl bromide or aryl iodide to bis-ligated palladium(0) complexes of bulky, trialkylphosphines or to Pd(dba)2 (dba = dibenzylidene acetone) in the presence of 1 equiv of phosphine produced the corresponding arylpalladium(II) complexes in good yields. In contrast, oxidative addition of phenyl chloride to the bis-ligated palladium(0) complexes did not produce arylpalladium(II) complexes. The oxidative addition of phenyl triflate to PdL2 (L = 1-AdPtBu2, PtBu 3, or Q-phos) also did not form arylpalladium(II) complexes. The reaction of silver triflate with (1-AdPtBu2)Pd(Ph)Br furnished the corresponding arylpalladium(II) triflate in good yield. The oxidative addition of phenyl bromide and iodide to Pd(Q-phos)2 was faster than oxidative addition to Pd(1-AdPtBu2)2 or Pd(PtBu3)2. Several of the arylpalladium complexes were characterized by X-ray diffraction. All of the arylpalladium(II) complexes are T-shaped monomers. The phenyl ligand, which has the largest trans influence, is located trans to the open coordination site. The complexes appear to be stabilized by a weak agostic interaction of the metal with a ligand C-H bond positioned at the fourth-coordination site of the palladium center. The strength of the Pd…H bond, as assessed by tools of density functional theory, depended upon the donating properties of the ancillary ligands on palladium.

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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 syntheses, characterisation and crystal structure (when X = Br) of [Pd4(mu3-CF)(mu-X)3(PBut 3)4] (X = Cl, Br) are reported; the mu3-CF moiety is hydrogenated to CFH3 under mild conditions and serves as a model for the heterogeneous hydrogenation of CFCs to HCFCs.

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