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Pd0-mediated rapid coupling of methyl iodide with excess amounts of benzyl- and cinnamylboronic acid esters: Efficient method for incorporation of positron-emitting 11C radionuclide into organic frameworks by coupling between two sp3-hybridized carbons

Pd0-mediated rapid cross coupling between sp3- hybridized carbons of CH3I and benzyl- or cinnamylboronic acid esters using [Pd{P(tert-C4H9)3}2]/CsF in DMF/H2O gave the corresponding methylated compounds in high yield. The utility was well demonstrated for the synthesis of short-lived PET tracer, N-(4-[11C]ethylphenyl)propionamide, in 90 ± 1% radio-HPLC analytical yield and 49 ± 3% radiochemical yield.

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

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Zerovalent palladium and platinum complexes of aminomethylphosphines. Crystal structure of the palladium(0) dibenzylideneacetone complex >

Tris(dibenzylideneacetone)dipalladium and bis(dibenzylideneacetone)platinum react with N, N-bis(dicyclohexylphosphinomethyl)methylamine, (Cy2PCH2)2NMe (Cy = cyclohexyl), and with N, N-bis(diphenylphosphinomethyl)methylamine, (Ph2PCH2)2NMe (Ph = phenyl), to give the complexes > (M = Pd or Pt, dba = dibenzylideneacetone), R = Cy or Ph.The zerovalent platinum complex > can be obtained by hydrazine hydrate reduction of a mixture of > and triphenylphosphine or oneof cis- and (Cy2PCH2)2NMe.Thecrystal structure of > has been determined and some reactions of the complexes are reported.Keywords: Palladium; Platinum; Aminomethylphosphines; Dibenzylideneacetone; Crystal structure

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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 cross-coupling between in situ generated allenyl/propargyl-lithium species and aryl bromides to yield highly functionalized allenes is reported. The direct and selective formation of allenic products preventing the corresponding isomeric propargylic product is accomplished by the choice of SPhos or XPhos based Pd catalysts. The methodology avoids the prior transmetalation to other transition metals or reverse approaches that required prefunctionalization of substrates with leaving groups, resulting in a fast and efficient approach for the synthesis of tri- and tetrasubstituted allenes. Experimental and theoretical studies on the mechanism show catalyst control of selectivity in this allene 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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Enantioselective intramolecular dearomative Heck reactions have been developed by Pd-catalyzed cross-coupling of aryl halides or aryl triflates with the internal C=C bond of indoles, benzofurans, pyrroles, and furans. A variety of structurally unique spiroheterocycles and benzofused heterocycles having N/O-substituted quaternary carbon stereocenters, and exocyclic olefin moieties were afforded in moderate to excellent yields with good to excellent enantioselectivities, showing a broad scope of the present protocol. A series of new BINOL- and H8-BINOL-based phosphoramidite ligands were synthesized and proved to be efficient chiral ligands in the reactions of C2-tethered substrates to form spiroheterocycles. (S)-SEGPHOS turned out to be a good ligand for the reaction delivering benzofused indolines and pyrrolines. Synthetic applications based on transformations of the exocyclic double bonds were realized without loss of enantiopurities, including hydrogenation, hydroborylation, and stereospecific ring-expanding rearrangement.

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

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New highly active heterogeneous silicaethylphosphatrioxaadamantane palladium catalysts with very low millimole per gram palladium load are reported. Applied to a broad range of Suzuki substrate pairs in 0.1-0.2 mol%, these catalysts are very effective, reusable and resistant to leaching for reactions in hot xylene or with microwave irradiation of EtOH:H2O:DME solutions.

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

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Reaction conditions for the three-component synthesis of aryl 1,3-diketones are reported applying the palladium-catalyzed carbonylative alpha-arylation of ketones with aryl bromides. The optimal conditions were found by using a catalytic system derived from [Pd(dba)2] (dba=dibenzylideneacetone) as the palladium source and 1,3-bis(diphenylphosphino)propane (DPPP) as the bidentate ligand. These transformations were run in the two-chamber reactor, COware, applying only 1.5 equivalents of carbon monoxide generated from the CO-releasing compound, 9-methylfluorene-9-carbonyl chloride (COgen). The methodology proved adaptable to a wide variety of aryl and heteroaryl bromides leading to a diverse range of aryl 1,3-diketones. A mechanistic investigation of this transformation relying on 31P and 13C NMR spectroscopy was undertaken to determine the possible catalytic pathway. Our results revealed that the combination of [Pd(dba)2] and DPPP was only reactive towards 4-bromoanisole in the presence of the sodium enolate of propiophenone suggesting that a [Pd(dppp)(enolate)] anion was initially generated before the oxidative-addition step. Subsequent CO insertion into an [Pd(Ar)(dppp)(enolate)] species provided the 1,3-diketone. These results indicate that a catalytic cycle, different from the classical carbonylation mechanism proposed by Heck, is operating. To investigate the effect of the dba ligand, the Pd0 precursor, [Pd(eta3-1-PhC 3H4)(eta5-C5H5)], was examined. In the presence of DPPP, and in contrast to [Pd(dba)2], its oxidative addition with 4-bromoanisole occurred smoothly providing the [PdBr(Ar)(dppp)] complex. After treatment with CO, the acyl complex [Pd(CO)Br(Ar)(dppp)] was generated, however, its treatment with the sodium enolate led exclusively to the acylated enol in high yield. Nevertheless, the carbonylative alpha-arylation of 4-bromoanisole with either catalytic or stoichiometric [Pd(eta3-1-PhC3H4) (eta5-C5H5)] over a short reaction time, led to the 1,3-diketone product. Because none of the acylated enol was detected, this implied that a similar mechanistic pathway is operating as that observed for the same transformation with [Pd(dba)2] as the Pd source. CO-operation is the key! The first palladium-catalyzed carbonylative alpha-arylation of aryl bromides is described. A wide array of different aryl 1,3-diketones can be isolated in good-to-excellent yields using only stoichiometric amounts of CO (see scheme). A mechanistic study is presented that suggests the need for enolate coordination prior to oxidative addition when [Pd(dba)2] is employed as the precatalyst. 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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Oxidative addition of pyridyl-functionalised 4-iodoimidazolium salts to palladium(0) gives catalytically active complexes in which the N-heterocyclic carbene is bound to the palladium(ii) centre in a non-classical bonding mode via C(4). The Royal Society of Chemistry 2006.

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

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Palladium(0)-catalyzed reaction of allene-substituted allylic carboxylates 3-8 employing 2-5 mol % of Pd(dba)2 in refluxing toluene leads to the carbocyclization and elimination of carboxylic acid to give bicyclo[4.3.0]nonadiene and bicyclo[5.3.0]decadiene derivatives (12-17). The carbon-carbon bond formation is stereospecific, occurring syn with respect to the leaving group. Addition of maleic anhydride as a ligand to the above-mentioned procedures changed the outcome of the reaction, and under these conditions 3-5 afforded cycloisomerized products 21-23. The experimental results are consistent with a mechanism involving oxidative addition of the allylic carboxylate to Pd(0) to give an electron-deficient (pi-allyl) palladium intermediate, followed by nucleophilic attack by the allene on the face of the pi-allyl opposite to that of the palladium atom. Furthermore, it was found that the Pd(dba)2-catalyzed cyclization of the trans-cycloheptene derivative (trans-8) can be directed to give either the trans-fused (trans-17) or the cisfused (cis-17) ring system by altering the solvent. The former reaction proceeds via a nucleophilic transallene attack on the (pi-allyl)palladium intermediate, whereas the latter involves a syn-allene insertion into the allyl-Pd bond of the same intermediate. The products from the carbocylization undergo stereoselective Diels-Alder reactions to give stereodefined polycyclic systems in 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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We describe a new approach to acid chloride synthesis via the palladium-catalyzed carbonylation of aryl iodides. The combination of sterically encumbered phosphines (PtBu3) and CO coordination has been found to facilitate the rapid carbonylation of aryl iodides into acid chlorides via reductive elimination from (tBu3P)(CO) Pd(COAr)Cl. The formation of acid chlorides can also be exploited to perform traditional aminocarbonylation reactions under exceptionally mild conditions (ambient temperature and pressure), and with a range of weakly nucleophilic substrates.

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

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Stoichiometric and catalytic conversion of alkynes to conjugated (Z,Z)-dienes and cyclopentadienes via palladacyclopentadienes and 1,3-dienylpalladium(II) halide and triorganopalladium(IV) halide compounds containing chelating nitrogen ligands

Palladacyclo-2,4-pentadiene compounds containing a chelating bidentate nitrogen ligand Pd{(C(E)=C(E)-C(E)=C(E)}(NN) 1a-f (E = CO2Me, NN = Ph-bip, Ar-bian, bpy, dcm-bpy, bpym) and 2a,b (E = CF3, NN = Ph-bip, (p-tol)-bian) have been prepared from Pd(dba)2, the appropriate bidentate N-ligand, and electron-deficient acetylenes dimethyl 2-butynedioate or hexafluorobutyne. X-ray crystal structures were obtained for compounds 1a (NN = Ph-bip) and Id (NN = 2,2?-bpy). In solution, an equilibrium between the monomer and a dimer exists for compounds 1d and 1e (NN = bipyrimidine); in the solid state, 1d is a monomer. The dimeric form of 1d is of the same type as the zerovalent palladium compound [(mu-3,3?-dicarbomethoxy-2,2?-bipyridine)Pd(tcne)]2 in which the two bipyridine derivatives bridge between the two palladium centers, as determined from the X-ray crystal structure of this compound (7). The palladacycles 1 undergo oxidative addition of methyl iodide, benzyl bromide, or iodobenzene. Subsequent reductive elimination gives rise to the formation of 4-functionalized 1,3-dienylpalladium(II) halide compounds 3-5 (cis arrangement of the ester functions at the double bonds). In the reaction with an excess of 1,4-chloro-2-butyne, a trimerization took place forming 1-(1?-chloroethenyl)-1,2,3,4,5-pentakis(chloromethyl)-2,4-cyclopentadiene (6). Employing the established kinetic compatibility of the formation of the palladacycles with a successive oxidative addition/reductive elimination of organic halides and subsequent transmetalation with tetramethyltin, a catalytic cycle for the three-component synthesis of (Z,Z)-dienes of the type R-C(E)=C(E)C(E)=C(E)CH3 (8, R = alkyl, aryl; E=CO2CH3) has been conceived, e.g., from dimethyl 2-butynedioate, an organic halide, and tetramethyltin employing 1% of 1b as the catalyst in DMF. This constitutes the first catalytic synthesis of conjugated dienes from alkynes. Pd(phosphine) compounds do not catalyze this reaction.

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