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o-Iodophenols and o-iodoaniline derivatives react with terminal alkynes under 1 atm of CO in the presence of pyridine and catalytic amounts of Pd(OAc)2 to generate coumarins and 2-quinolones, respectively, as the only products. Terminal alkynes bearing alkyl, aryl, silyl, hydroxyl, ester and cyano substituents are effective in these processes affording the desired products in moderate yields. The formation of coumarins and 2-quinolones in this process is in stark contrast with all previously described palladium-catalyzed reactions of o-iodophenols or o-iodoanilines with terminal alkynes and CO, which have afforded chromones and 4-quinolones. Moreover, under our reaction conditions terminal alkynes insert into the carbon-palladium bond instead of undergoing a Sonogashira-type coupling as confirmed by an isotope labeling experiment.

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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 generation of PNP compounds bearing different diarylphosphine groups were prepared and used as ligands in palladium-catalysed Suzuki cross-coupling reactions. Rates of oxidative addition of iodobenzene to (PNP)Pd[o] complexes were measured using UV spectroscopy. Synergistic effects between the N- and P- substituents were identified and correlated in redox and catalytic chemistry.

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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 facile and site-selective C-H bond fluorination of phenols using removable 2-pyridyloxy group as an auxiliary was developed. Alternatively, late-stage C-H bond fluorination of bioactive 2-phenoxyl nicotinate derivatives and diflufenican were also feasible under the present strategy.

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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 compound of formula I STR1 wherein X is sulfur or CH2 ; R1 is hydrogen, hydroxy, amino, C1-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, phenyl optionally substituted with one to three C1-6 alkyl, C1-6 alkyloxy or hydroxy, C1-6 alkylthio, phenylthio optionally substituted with one to three C1-6 alkyl or C1-6 alkyloxy on the phenyl ring, phenylmethyloxy optionally substituted with one to three C1-6 alkyl or C1-6 alkyloxy on the phenyl ring, 1-morpholino, C1-6 alkyloxy, C2-6 alkenylmethyloxy, C3-6 alkynylmethyloxy, C1-6 alkylamino, C1-6 dialkylamino or a radical selected from the group consisting of STR2 in which n is 0 to 3, R5 is C1-6 alkyl or hydrogen, and R3 and R4 are independently C1-6 alkyl; R2 is hydrogen, a conventional amino protecting group or an acyl group; R0 is hydrogen or a conventional carboxy protecting group, or –CO2 R0 taken together forms a physiologically hydrolyzable ester; or pharmaceutically acceptable salts or solvates thereof.

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

Brief introduction of Bis(dibenzylideneacetone)palladium

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The heavy-atom heterocycle Pd[Re2(CO)8(mu-SbPh2)(mu-H)]2 (5) has been synthesized by the palladium-catalyzed ring-opening cyclodimerization of the three-membered heterocycle Re2(CO)8(mu-SbPh2)(mu-H) (3). The Pd atom occupies the center of the ring. The Pd atom in 5 can be removed reversibly to yield the palladium-free heterocycle [Re2(CO)8((mu-SbPh2)(mu-H)]2 (6).

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

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Stereoselective synthesis of 2-substituted dehydropiperidinones and their further transformation to variously disubstituted piperidine derivatives was achieved employing D-arabinopyranosylamine as the stereodifferentiating carbohydrate auxiliary. A domino Mannich-Michael reaction of 1-methoxy-3-(trimethylsiloxy)butadiene (Danishefsky’s diene) with O-pivaloylated arbinosylaldimines furnished N-arabinosyl dehydropiperidinones in high diastereoselectivity. Subsequent conjugate cuprate addition gave 2,6-cis-substituted piperidinones, while enolate alkylation furnished 2,3-trans-substituted dehydropiperidinones. Electrophilic substitution at the enamine structure afforded 5-nitro- and 5-halogen dehydropiperidinones of which the latter were applied in palladium-catalyzed coupling reactions. The absolute configuration of the obtained products was proven by NMR and X-ray structure analysis as well as by syntheses of the alkaloids (+)-coniine and (+)-dihydropinidine.

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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 collection of fourteen diphenylamine macrocyclic derivatives containing a peptide chain with different substituents was synthesized using a protocol of two Ugi four component reactions (Ugi-4CR) and a Buchwald-Hartwig macrocyclization. Their anti-inflammatory effects were assayed with an ear edema model using 12-O-tetradecanoylphorbol-13-acetate, while the activity of myeloperoxidase was determined to evaluate the index of leukocyte infiltration. Compound 5e had an ID50 of 0.18 muM per ear with a potency higher than that of the reference drugs indomethacin and celecoxib (0.24 and 0.91 muM per ear, respectively). Moreover, the cytotoxicity of the macrocycles was determined in two healthy cell lines, showing a low percentage of toxicity.

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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 method has been developed for the chemo- and stereoselective Suzuki-Miyaura cross-coupling of optically enriched gem-diboronyl compounds with various aryl bromides. Experimental evidence suggests that the Lewis acidity of the second boron group in these substrates plays a significant role in facilitating these otherwise challenging cross-coupling processes. beta-Diboronyl esters may be successfully cross-coupled in excellent yield and enantiomeric excess with prior conversion of the pinacol boronate to the corresponding trifluoroborate salt. In contrast, a substrate bearing a Weinreb amide can undergo direct coupling of the Bpin moiety, likely due to the stronger coordination of the more basic amide carbonyl group. The resulting optically enriched secondary boronate may be used in a second enantioselective cross-coupling to afford pharmaceutically relevant diarylmethane products. The use of a Weinreb amide substrate allows for facile postcoupling modification, as demonstrated by a transformation to the corresponding ketone.

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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 class of O2-alkyl derived diazeniumdiolates 3a-f and 4a-c were designed and synthesized as new bioorthogonal NO precursors, which can be effectively uncaged in the presence of a palladium catalyst via bioorthogonal bond cleavage reactions to generate NO in living cancer cells, eliciting potent antiproliferative activity.

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

Properties and Exciting Facts About Bis(dibenzylideneacetone)palladium

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The complexes and react with 2,6-dichloropyridine at high temperature to give trans-(PPh3)2> (M=Pd, Ia; M=Pt, Ib).Ligand substitution reactions of these complexes with 1,2-bis(diphenylphosphino)ethane, dimethyldithiocarbamate, and LiBr have been carried out, and also insertion of CO into the Pd-C bond of Ia.Oxidation of Ia with H2O2, giving the dimeric complex (PPh3)>2 is also reported.The complex analogous to Ia but containing PMePh2 in place of PPh3 has been obtained by oxidative addition to the Pd(dba)2/PMePh2 system (dba=dibenzylideneacetone).

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