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Palladium-catalyzed oxidative carbonylation of 1-alkynes into 2-alkynoates with molecular oxygen as oxidant

A new preparative method to produce alkyl 2-alkynoates from 1-alkynes in alcohol under atmospheric pressure of CO at room temperature was developed with palladium-phosphine catalysts, using molecular oxygen as an oxidant. On the basis of the behavior of model complexes such as methoxycarbonylpalladium and alkynylpalladium complexes, we propose a mechanism accounting for the catalytic carbonylation of alkynes through an intermediate having the both methoxycarbonyl and alkynyl ligands that liberates methyl 2-alkynoates and a Pd(0) species on reductive elimination. The oxidation of Pd(0) to Pd(II) species in the presence of a halide ion was confirmed to proceed cleanly with molecular oxygen as the oxidant. On the basis of the findings on homogeneous catalysts, a heterogeneous catalytic system using Pd/C has also been developed.

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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 Synthesis and Reactions of Palladium-Iron Carbonyl Complexes containing Bridging Ph2PCH2PPh2 Ligands

Treatment of tetrahydrofuran solution of FeI2 with two equivalents of Ph2PCH2PPh2 (dppm),under an atmosphere of CO, gave trans,mer- (1b) in high yield.The bromide analogue was prepared similarly but was unstable.Treatment of compound (1b) with (dba = dibenzylideneacetone) in benzene, under an atmosphere of CO, gave the bimetallic iron(I)-palladium(I) complex (2c).Complex (2c) was protonated by HBF4*OEt2 to give the cationic hydride BF4, wich was characterised only in solution.Treatment of (2c) with MeCN caused displacemeent of both iodide and carbonyl ligands from iron to give <(MeNC)3Fe(mu-dppm)2PdI>I, whereas treatment of (2c) with the bulky isocyanide ButNC displaced only iodide to give <(ButNC)(OC)2Fe(mu-dppm)2PdI>I.N.m.r. (1H- and 31P-<1H>)Nand i.r. data are reported.

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

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Regiospecific alkyne-formate ester reactions catalyzed by palladium(0)

Metal-catalyzed reactions of unsaturated substrates and formate esters have been the subject of a number of recent publications and patents, the focus being on olefins. We have now found that palladium(0) can catalyze the regiospecific conversion of alkynes and formate esters to trans-alpha, beta-unsaturated esters. Five alkynes and four esters were employed in the reaction experiments. For example: No reaction occurs when phenylacetylene is treated with n-butyl formate and a catalytic amount of bis(dibenzylideneacetone) paladium(0) in toluene at 80 atm carbon monoxide for 3 days at 100C. However, repetition of the reaction with added 1,4-bis(diphenylphosphino)butane results in the isolation of trans-n-butyl cinnamate in 31% yield. A possible mechanism for the alkyne-formate ester reaction is outlined.

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

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Pd/Pt metallacyclopropa[60]fullerene complexes bearing versatile phosphorous ylide ligands; a comprehensive multi-spectroscopic, electrochemistry, theoretical and catalytic studies

The synthesis of new Pd/Pt metallacyclopropa[60]fullerene complexes containing unsymmetrical phosphorus ylides [Ph2P(CH2)nPPh2 = C(H)C(O)C6H4-p-OMe] (n = 1, (Y1); n = 2, (Y2)) has been reported. The synthesized complexes exhibit different structures, including two P,C? chelated [(eta2-C60)Pd(kappa2-Y1)] (1) and [(eta2-C60)Pt(kappa2-Y1)] (2) complexes and two P-coordinated [(eta2-C60)Pd(Y2)2] (3) and [(eta2-C60)Pt(Y2)2] (4) complexes with chain structures. Characterization of all compounds was performed by multi-neclear NMR spectroscopies (1H, 13C and 31P NMR) and other conventional techniques such as IR, UV?Vis, SEM and cyclic voltammetry (CV) analyses. In this regard, the presence of all characteristic chemical shifts in the IR and NMR spectra proposed the formation of desired products. Also, theoretical studies were used to investigate the nature of metal?ligands in all complexes. In addition, a comparison between the catalytic activity of Pd complexes 1 and 3 was evaluated in the Suzuki-Miyaura reaction of various aryl chlorides with phenylboronic acid, which revealed a meaningful difference between the catalytic activity of complexes 1 and 3.

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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 Palladium(II)-Catalyzed Oxidative Aminofluorination of Unactivated Alkenes with Et4NF?3 HF as a Fluoride Source

The first asymmetric PdII-catalyzed aminofluorination of unactivated alkenes using chiral quinoline-oxazolines (Quox) as ligands has been developed. This reaction provides easy access to a wide array of enantiomerically enriched beta-fluoropiperidines in good yields and with excellent enantioselectivity. Notably, Et4NF?3 HF as a readily accessible nucleophilic fluoride source was found to play an essential role in the enantioselective control, and CsOCF3 also acts a key additive to improve the excellent ee value of products.

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

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Water Soluble, Zero-valent, Platinum-, Palladium-, and Nickel-P(CH2OH)3 Complexes: Catalysts for the Addition of PH3 to CH2O

The phosphine P(CH2OH)3 forms water soluble complexes of the type 4> (M=Pt, Pd, or Ni) which are catalysts for the addition of PH3 to CH2O and the Pt complex is readily protonated by water; the crystal structure of the Pd complex is 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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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