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We report herein a facile approach to tetrahydropyridazines, a scaffold found in many natural products and biologically active entities, via Pd-catalyzed carboamination of readily available alkenyl hydrazones with aryl and alkenyl halides. Preliminary studies showed its promise for enantioselective synthesis. This work offers an expedient access to the tetrahydropyridazine scaffold bearing substitution patterns, thus significantly increasing the availability of these derivatives for downstream evaluation.

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

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Carbon-nitrogen bond-forming cross-coupling reaction of haloarenes with N-trimethylsilyl (TMS)-substituted secondary and primary arylamines proceeded with the aid of a palladium catalyst and a fluoride activator. Various TMS-N(aryl)2, TMS-NH(aryl), and TMS-N(alkyl)2 reacted to give the corresponding coupled products in high yields. Multi-TMS-amine nucleophiles such as N,N-(TMS)2-aniline and N,N?-Ph2-N,N?-(TMS)2-p-phenylenediamine also participated in this C-N coupling to give multiply C-N coupled products in high yields. The novel C-N cross-coupling reaction was successfully applied to C-N bond-forming polymerization. Relative rates of the cross-coupling of p-bromotoluene with N-TMS-substituted primary and secondary amines showed that N-TMS-diphenylamine reacted faster than N-TMS-N-methylaniline or N-TMS-aniline, and N-TMS-morpholine was the least reactive, indicating that the low basicity of the nitrogen nucleophile is the key for the smooth coupling.

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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 fluorescence chemsensor for carbon monoxide (CO), based on transformation of weakly fluorescent iodide to strong fluorescent amino product upon reacting with CO, shows abilities of quantitative measurement of CO in air at a level of 50-1000 ppm and real-time and on-site monitoring for CO flammation/explosion.

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

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Synthetic Route of 32005-36-0, Because a catalyst decreases the height of the energy barrier, its presence increases the reaction rates of both the forward and the reverse reactions by the same amount.32005-36-0, Name is Bis(dibenzylideneacetone)palladium, molecular formula is C34H28O2Pd. In a article,once mentioned of 32005-36-0

A combination of an enantioselective conjugate addition/trapping sequence and a ruthenium(iii)-catalyzed domino cyclization provides a concise access to benzo[d]xanthenes found in several anti-influenza active sesquiterpene natural 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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Inhibition of sodium glucose cotransporter 2 (SGLT2) has been proposed as a novel therapeutic approach to treat type 2 diabetes. In our efforts to discover novel inhibitors of SGLT2, we first generated a 3D pharmacophore model based on the superposition of known inhibitors. A search of the Cambridge Structural Database using a series of pharmacophore queries led to the discovery of an O-spiroketal C-arylglucoside scaffold. Subsequent chemical examination combined with computational modeling resulted in the identification of the clinical candidate 16d (CSG452, tofogliflozin), which is currently under phase III clinical trials.

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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 Buchwald-type diphosphine ligand has been developed for applications in Pd-catalyzed amination reactions towards the preparation of triarylamines. The catalyst can be used to perform the amination of a diverse array of aryl and heteroaryl chlorides.

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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 series of monomeric arylpalladium(II) complexes LPd(Ph)X (L = 1-AdP tBu2, PtBu3, or Ph 5FcPtBu2 (Q-phos); X = Br, I, OTf) containing a single phosphine ligand have been prepared. Oxidative addition of aryl bromide or aryl iodide to bis-ligated palladium(0) complexes of bulky, trialkylphosphines or to Pd(dba)2 (dba = dibenzylidene acetone) in the presence of 1 equiv of phosphine produced the corresponding arylpalladium(II) complexes in good yields. In contrast, oxidative addition of phenyl chloride to the bis-ligated palladium(0) complexes did not produce arylpalladium(II) complexes. The oxidative addition of phenyl triflate to PdL2 (L = 1-AdPtBu2, PtBu 3, or Q-phos) also did not form arylpalladium(II) complexes. The reaction of silver triflate with (1-AdPtBu2)Pd(Ph)Br furnished the corresponding arylpalladium(II) triflate in good yield. The oxidative addition of phenyl bromide and iodide to Pd(Q-phos)2 was faster than oxidative addition to Pd(1-AdPtBu2)2 or Pd(PtBu3)2. Several of the arylpalladium complexes were characterized by X-ray diffraction. All of the arylpalladium(II) complexes are T-shaped monomers. The phenyl ligand, which has the largest trans influence, is located trans to the open coordination site. The complexes appear to be stabilized by a weak agostic interaction of the metal with a ligand C-H bond positioned at the fourth-coordination site of the palladium center. The strength of the Pd…H bond, as assessed by tools of density functional theory, depended upon the donating properties of the ancillary ligands on palladium.

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

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Mononuclear phosphine sulfide Pd(0) complexes and a polymer-supported triphenylphosphine sulfide Pd(0) complex were prepared as new air-stable Pd(0) catalysts for C-C coupling reactions. The phosphine sulfide Pd(0) complexes are not decomposed after completion of Suzuki-Miyaura coupling, and the polymer-supported Pd(0) catalyst is practically recyclable, while phosphine Pd(0) complexes are decomposed into inactive Pd(0) black after consuming the substrates. New catalytic activity of Pd(0) that promotes chalcogen atom replacement of phosphine chalcogenides (R3P=X, X = O, S, Se) is reported. A mechanistic study revealed that the new catalytic chalcogen replacement results from activation of the P=X bond as well as promotion of the oxidative chalcogenide formation. The intermediate phosphine was successfully trapped as a phosphine Pd(II) complex, and the P=X bond activation is applicable to regeneration of phosphine or phosphine sulfide from oxidized phosphine.

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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 set of model compounds have been designed in order to develop useful synthetic routes to novel dendritic carbosilane molecules functionalized with organometallic complexes derived from the monoanionic [C6H3(CH2NMe2)2-2,6] – (=NCN) and [C6H4(CH2NMe2)-2]- (=CN) ligands. Selective electrophilic palladation of both [C6H2(CH2NMe2) 2-2,6-(SiMe3)2-1,4] (1) and [C6H4(CH2NMe2)-4-SiMe3-1] (6) using Pd(OAc)2 afforded, after addition of LiCl, [PdCl-(C6H2{CH2NMe2} 2-2,6-SiMe3-4)] (2) and dimeric [PdCl(C6H3{CH2NMe2}-2-SiMe 3-5)]2 (7), respectively, in 98% and 84% yield. Lithiation of [C6H3(CH2NMe2) 2-3,5SiMe3-1] followed by transmetalation using 1 equiv of PtCl2(SEt2)2 in THF at room temperature yielded the platinated complex [PtCl(C6H2{CH2NMe2} 2-2,6-SiMe3-4)] (3). Reaction of the iodinated analogue of 1, [IC6H2(CH2NMe2) 2-2,6-SiMe3-4] (4), with an excess of Ni(PPh3)4 in THF at room temperature afforded the nickel complex [NiI(C6H2{CH2NMe}2-2,6-SiMe 3-4)] (5). Similar synthetic approaches have also been applied to the (N)CN-substituted carbosilane ligand systems [CH2Si(Me)2C6H3(CH 2NMe2)2-3,5]2 and [CH2Si(Me)2C6H4(CH 2NMe2)-4]2 to give the bismetalated species [CH2Si(Me)2C6H2(CH 2NMe2)2-3,5-(MX)-4]2 (MX = PdCl (9), PtCl (10), PdI (12)) and [CH2Si(Me)2C6H3(CH 2NMe2)-4-(PdCl)-3]2 (13) in good yields. The molecular structures of 5 and bispalladated 13 have been determined. The molecular structure of 13 shows this species to be a centrosymmetric dimeric aggregate in the solid state, with the two bis(amino)arylpalladium carbosilane molecules held together via two terminal – terminal chlorine bridging atoms, thus forming a 26-membered macrocyclic ring.

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

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Intermolecular Heck reaction of common alkyl halides, a longstanding problem in palladium catalysis, is realized with a simple Pd/dppf catalyst. Both primary and secondary alkyl halides are suitable for coupling with aromatic olefins. Single electron transfer from (dppf)Pd0 to alkyl halide initiated the catalytic cycle and gave alkyl radicals. This journal is the Partner Organisations 2014.

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