A new application about Bis(dibenzylideneacetone)palladium

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A general and practical palladium-catalyzed direct a-arylation of amides with aryl halides

An efficient system for the direct catalytic intermolecular alpha-arylation of acetamide derivatives with aryl bromides and chlorides is presented. The palladium catalyst is supported by Kwong’s indolebased phosphine ligand and provides monoarylated amides in up to 95% yield. Excellent chemoselectivities (>10:1) in the mono- and diarylation with aryl bromides were achieved by careful selection of bases, solvents, and stoichiometry. Under the coupling conditions, the weakly acidic alpha-protons of amides (pK a up to 35) were reversibly depotonated by lithium tert-butoxide (LiO-t-Bu), sodium tert-butoxide (NaO-t-Bu) or sodium bis(trimethylsilyl)amide [NaN(SiMe3)2].

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

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Synthesis, Characterization, and Reactivity of Palladium Fluoroenolate Complexes

Cross-coupling reactions of aryl groups with alpha-fluoro carbonyl compounds catalyzed by palladium complexes have been reported, but palladium fluoroenolate intermediates relevant to such reactions have not been isolated or even detected previously. We report the synthesis, structural characterization, and reactivity of a series of C-bound arylpalladium fluoroenolate complexes ligated by monophosphines and bisphosphines. DPPF-ligated arylpalladium fluoroenolate complexes (DPPF = 1,1-bis(diphenylphosphino)-ferrocene) derived from a monofluoroester, a difluoroester, difluoroamides, and difluoroacetonitrile underwent reductive elimination in high yields. Reductive elimination was faster from complexes containing less electron-withdrawing fluoroenolate groups and longer Pd-C(enolate) bonds than from complexes containing more electron-withdrawing fluoroenolate groups and shorter Pd-C(enolate) bonds. The rates of reductive elimination from these C-bound fluoroenolate complexes were significantly faster than those of the analogous trifluoromethyl complexes.

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

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Mechanistic Studies on a Cooperative NHC Organocatalysis/Palladium Catalysis System: Uncovering Significant Lessons for Mixed Chiral Pd(NHC)(PR3) Catalyst Design

A comprehensive investigation of the mechanism of the highly enantioselective Pd(PPh3)4/NHC-catalyzed annulation of vinyl benzoxazinanones and enals has been conducted. A study of reaction orders supports the postulated cooperative catalysis. Interestingly, a detailed investigation of the catalytically active palladium species pointed toward a dual role of the NHC acting as an organocatalyst and forming a novel mixed ligand Pd/NHC/phosphine complex. The catalytically active Pd/NHC/phosphine complex represents a new class of chiral palladium catalyst. Remarkably, phosphine plays a crucial role in this transformation. These complexes could be characterized by X-ray crystallographic analysis and employed as catalysts for the enantioselective [4 + 1] annulation reaction of vinyl benzoxazinones and sulfur ylides in good yields and good enantioselectivities.

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

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Palladium-catalyzed reactions of arylboron compounds with carboxylic acid chlorides

Reactions of sodium tetraarylborates and arylboronic acids with acyl chlorides in the presence of palladium salts afford non-symmetrical ketones in high yields under mild conditions.

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

The important role of Bis(dibenzylideneacetone)palladium

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Palladium-catalyzed carbonylative alpha-arylation of 2-oxindoles with (Hetero)aryl bromides: Efficient and complementary approach to 3-acyl-2-oxindoles

An efficient Pd-catalyzed carbonylative alpha-arylation of 2-oxindoles with aryl and heteroaryl bromides for the one-step synthesis of 3-acyl-2-oxindoles has been developed. This reaction proceeds efficiently under mild conditions and is complementary to the more common oxindole forming reactions. The transformation only requires a mild base and provides good to excellent yields even with heteroaromatic substrates. Employing a near stoichiometric amount of 13COgen, the methodology was easily extended to [13C] acyl labeling. The general applicability of the reaction conditions was demonstrated in the synthesis of a structure related to the pharmaceutically active 3-acyl-2-oxindoles, tenidap. Carbonylate it. 3-Acyl-2-oxindoles are directly obtained through an efficient Pd-catalyzed carbonylative alpha-arylation of 2-oxindoles with aryl and heteroaryl bromides. Only a mild base is required for the deprotonation and good to excellent yields are obtained even with heteroaromatic substrates.

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

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Design and synthesis of alpha-carboxy nucleoside phosphonate analogues and evaluation as HIV-1 reverse transcriptase-targeting agents

The synthesis of the first series of a new class of nucleoside phosphonate analogues is described. Addition of a carboxyl group at the alpha position of carbocyclic nucleoside phosphonate analogues leads to a novel class of potent HIV reverse transcriptase (RT) inhibitors, alpha-carboxy nucleoside phosphonates (alpha-CNPs). Key steps in the synthesis of the compounds are Rh-catalyzed O-H insertion and Pd-catalyzed allylation reactions. In cell-free assays, the final products are markedly inhibitory against HIV RT and do not require phosphorylation to exhibit anti-RT activity, which indicates that the alpha-carboxyphosphonate function is efficiently recognized by HIV RT as a triphosphate entity, an unprecedented property of nucleoside monophosph(on)ates.

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

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New palladium (II) complex of SCN unsymmetric pincer-type ligand via oxidative addition

A new approach to the synthesis of benzothiophene-based palladium(II) complex of SCN unsymmetrical pincer-type ligand from iodocyclization of bis(methylthio)phenyl substituted ethynyl pyridine followed by oxidative addition of tris-(dibenzyledeneacetone) dipalladium(0) has been developed. The mechanistic implication of palladium complex reveals the practical evidence of oxidative addition step in Suzuki coupling reaction.

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

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Reversible carbonylation of cationic palladium 2,6-bis<(dimethylamino)methyl>pyridine complexes: the first X-ray structure of a cationic aroyl-palladium complex

(1-Naphthyl)<2,6-bis<(dimethylamino)methyl>pyridine>palladium(II) trifluoromethanesulphonate (1b, OTf) was prepared in 60 percent yield starting from bis(dibenzylideneacetone)palladium(0) (Pd(dba)2) and 1-iodonaphthalene. (1-Naphthoyl)<2,6-bis<(dimethylamino)methyl>pyridine>palladium(II) trifluoromethanesulphonate (2b, OTf), characterized by X-ray crystallography, was obtained by insertion of carbon monoxide into the palladium-carbon bond of 1b in acetone solution.This insertion process was shown to be reversible.

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

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Reaction of Tertiary Amines with Bis(benzonitrile)dichloropalladium(II). Formation and Crystal Structure Analysis of Di-mu-chloro-dichlorobis<2-(N,N-di-isopropyliminio)ethyl-C>dipalladium(II)

Reaction of PdCl2.2PhCN with ethyldi-isopropylamine, tri-n-butylamine, or triethylamine at ambient temperature gives good yields of the eta1-ylidic complexes (2) – (5).

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

The important role of Bis(dibenzylideneacetone)palladium

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Controlling olefin isomerization in the heck reaction with neopentyl phosphine ligands

The use of neopentyl phosphine ligands was examined in the coupling of aryl bromides with alkenes. Di-tert-butylneopentylphosphine (DTBNpP) was found to promote Heck couplings with aryl bromides at ambient temperature. In the Heck coupling of cyclic alkenes, the degree of alkene isomerization was found to be controlled by the choice of ligand with DTBNpP promoting isomerization to a much greater extent than trineopentylphosphine (TNpP). Under optimal conditions, DTBNpP provides high selectivity for 2-aryl-2,3-dihydrofuran in the arylation of 2,3-dihydrofuran, whereas TNpP provided high selectivity for the isomeric 2-aryl-2,5-dihydrofuran. A similar complementary product selectivity is seen in the Heck coupling of cyclopentene. Heck coupling of 2-bromophenols or 2-bromoanilides with 2,3-dihydrofurans affords 2,5-epoxybenzoxepin and 2,5-epoxybenzazepins, respectively.

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