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Alternative routes for the introduction of aldehyde functionality are particularly desirable for fine chemical and pharmaceutical intermediates because of the wide range of further transformations that are possible. Catalytic processes are of particular interest for minimising waste, and therefore the reductive carbonylation of aryl halides has been explored. We have shown that high yields of aldehydes may be obtained for a wide selection of aryl iodides and bromides using mild conditions (3 bar of CO, temperatures 60-120C) and silanes as hydride source. A choice of conditions (catalyst, base, solvent) is required to cover the range of aryl substituents varying in electron donation and steric influence. This is related to the competing needs of the several steps of this reaction, including oxidative addition, CO substitution, CO insertion, hydride transfer, and reductive elimination.

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

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With hepta-1,6-diene and diallyl ether, Pd0 and Pt0 form highly reactive homoleptic dinuclear M2(1,6-diene)3 complexes, which are cleaved by donors L (e.g. C2H4, phosphanes, phosphites, isonitriles) to afford mononuclear derivatives L-M(1,6-diene); the X-ray structure of (Me3P)Pd{(eta2-CH2=CHCH2) 2O} has been determined.

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

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Dimethyl acetylenedicarboxylate reacts with PdI(C6H3Me2-3,5)(bpy) in the presence of AgBF4, causing rapid insertion of three acetylene molecules into the Pd-C bond to afford [Pd{C(CCOOMe-CZ-CZ-CZ=CZ)(Z)(C6H3Me 2-3,5)}(bpy)]BF4 (Z = COOMe), whereas a similar reaction without AgBF4 gives the product of a single insertion of the carbon-carbon triple bond, Pd(I)(CZ=CZC6H3Me2-3,5)(bpy).

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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 regioselective palladation reactions of 3-substituted derivatives of 2-<(dimethylamino)methyl>naphthalene, C10H6(CH2NMe2)-2-R-3 (R=Cl, SiMe3 or OSiMe3), were studied.For the substrate with R=Cl, no cyclopalladation at position 1 was observed and the co-ordination complex was isolated.The 3-palladated product was formed in 10percent yield via C-Cl activation.The reaction of 2-<(dimethylamino)methyl>-3-methylnaphthalene with Pd(O2CMe)2 and work-up with LiCl did lead to palladation at position 1, the resulting complex being isolated in 96percent yield.The crystal structure of bis(acetonitrile) <2-<(dimethylamino)methyl>-3-methyl-1-naphthyl>palladium trifluoromethanesulfonate was solved.Monoclinic, space group P21/n, with a=13.193(1), b=11.801(1), c=14.797(1) Angstroem, beta=105.15(1) deg, Z=4.The structure was refined to R=0.042 for 3455 reflections with I > 2.5?(I).Palladation at position 1 was also achieved by oxidative addition of 1-bromo-2-<(dimethylamino)methyl>naphthalene to (dba=dibenzylideneacetone).Protection of C(3) with R=SiMe3 resulted in quantitative replacement of the SiMe3 group by palladium.Silicon-oxygen bond cleavage was observed when the substrate with R=OSiMe3 was treated with Pd(O2CMe)2.Palladium bis<3-<(dimethylamino)methyl>-2-naphtholate> was obtained quantitatively.Oxidation of several arylpalladium complexes with tBuO2H was achieved in the presence of (acac=acetylacetonate) or <2> (cod=cycloocta-1,5-diene) as catalyst.The corresponding 1-naphthols were prepared in yields varying from 33 to 78 percent.In a number of cases the corresponding 1,4-naphthoquinones were prepared in yields varying from 18 to 38percent.

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

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In homogeneous catalysis, the catalyst is in the same phase as the reactant. The number of collisions between reactants and catalyst is at a maximum.In a patent, 32005-36-0, name is Bis(dibenzylideneacetone)palladium, introducing its new discovery. COA of Formula: C34H28O2Pd

Three-component coupling reaction of acid chlorides, organodisilanes, and 1,3-dienes achieves 1,4-carbosilylation of the 1,3-dienes to afford allylic silanes as the product. Bis(dibenzylideneacetone)palladium, a naked Pd(0) complex without donating ligand, showed high catalytic activity. A carbon and a silicon substituent are introduced at 1- and 4-positions of the 1,3-dienes regio- and stereoselectively with concomitant decarbonylation of the acid chlorides. A wide variety of allylic silanes are synthesized in high yields from these easily accessible substrates. On the other hand, a bulky acid chloride such as adamantane-1-carboxylic acid chloride did not undergo the decarbonylation reaction but afforded allylic silanes containing acyl functionality. In all these reactions, transmetalation of the disilanes with eta3-allylchloropalladium intermediates might be a critical step in the catalytic cycle. As a model reaction for the transmetalation, reaction of di-mu-chlorobis[(1,2,3-eta)-4-phenyl-2-butenyl]dipalladium with disilanes was carried out. Although intermediate eta3-allylsilylpalladium species could not be detected, the corresponding allylic silanes, silyl chlorides, and Pd(0) metal were formed during the reaction. Furthermore, a similar three-component coupling reaction using aryl iodides, organosilylstannanes, and dienes also proceeded. However, the selectivity and the yield decreased considerably.

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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 first Pd-catalyzed Mizoroki-Heck-type reaction of [Ph2SRfn][OTf] with alkenes is described. The reaction of [Ph2SRfn][OTf] (Rfn = CF3, CH2CF3) with alkenes in the presence of 10 mol% Pd[P(t-Bu)3]2 and TsOH at room temperature provided the corresponding phenylation products in good to high yields. The bases that benefit the traditional Mizoroki-Heck reactions severely inhibited the transformation with [Ph2SRfn][OTf], whereas acids significantly improved the reaction. This protocol supplies a new class of cross-coupling partners for Mizoroki-Heck-type reactions and gains important insights into the reactivity of phenylsulfonium salts either with or without fluorine-containing alkyl groups as the promising phenylation reagents in organic synthesis.

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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 three-component coupling involving in situ generated arynes, terminal alkynes, and vinyl cyclopropane dicarboxylate has been developed. The process demonstrates the first example of aryne chemistry combined with the ring opening of vinyl cyclopropanes. This efficient method using readily available starting materials generates two new carbon-carbon bonds in one pot.

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

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Methods for the direct synthesis of difluoromethylated arenes are sparse, despite the importance of the difluoromethyl group in medical, agro-, and materials chemistry. A palladium-catalyzed decarbonylative cross-coupling reaction of acid chlorides with a difluoromethyl zinc reagent is achieved to access difluoromethylated compounds. The transformation proceeds at room temperature and shows broad functional group tolerance, thus providing a general and efficient method for decarbonylative difluoromethylation of a wide range of aromatic carboxylic 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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A catalytic intramolecular silapalladation of alkynes affords, in good yields and stereoselectively, syn-disilylated heterocycles of different chemical structure and size. When applied to silylethers, this reaction leads to vinylic silanols that undergo a rhodium-catalyzed addition to activated olefins, providing the oxa-Heck or oxa-Michael products, depending on the reaction 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 new type of catalytic process to convert carboxylic acids and organoboron compounds into unsymmetrical ketones in one-pot under mild and neutral conditions was presented. The method allowed the use of an alpha, beta-unsatuarted carboxylic acids such as trans-cinnamic acid. Benzoic acid was converted into 1,3-diphenyl-2-propyn-1-one when it was treated with dimethyl dicarbonate and phenylacetylene in the presence of Pd(OAc)2 and PPh3. The catalytic coupling reaction was considered to proceed through oxidative addition of the mixed anhydride produced from benzoic acid and dimethyl dicarbonate to give the acylpalladium intermediate.

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