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SUBSTITUTED MORPHOLINES AS MODULATORS FOR THE CALCIUM SENSING RECEPTOR

Compounds of Formula (I) along with processes for their preparation that are useful for treating, managing and/or lessening the diseases, disorders, syndromes or conditions associated with the modulation of calcium sensing (CaSR) receptors. Methods of treating, managing and/or lessening the diseases, disorders, syndromes or conditions associated with the modulation of calcium sensing (CaSR) receptors of Formula (I).

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

Simple exploration of 32005-36-0

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Direct cross-coupling access to diverse aromatic sulfide: Palladium-catalyzed double C-S bond construction using Na2S 2O3 as a sulfurating reagent

The Pd-catalyzed cross-coupling of aryl halides, alkyl halides, and Na 2S2O3·5H2O to deliver aromatic thioethers is described. Pyridine, furan, thiophene, benzofuran, benzoxazole, benzothiophene, benzothiazole, and pyrazine are all amenable to this protocol. The odorless and stable solid Na2S2O 3·5H2O was used as a convenient and environmentally friendly source of sulfur. Pd-catalyzed cross-couplings without thiols or thiophenols to build C-S bonds have not previously been achieved, which renders our observation more striking.

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

Some scientific research about Bis(dibenzylideneacetone)palladium

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Synthetic and structural studies on the transition-metal fullerene complexes (eta2-C60)M[(eta5-Ph 2PC5H4)2Ru]

A toluene solution of C60 reacted with an equimolar quantity of M(dba)2 (M = Pd, Pt; dba = dibenzylideneacetone) and (eta 5-Ph2PC5H4)2Ru or with M(PPh3)4 and (eta5Pb2PC 5H4)2Ru at room temperature to give the dinuclear transition-metal fullerene complexes (eta2-C 60)M[(eta5Ph2PC5H 4)2Ru] (1, M = Pd; 2, M = Pt), whereas the o-dichlorobenzene solution of C60 reacted with an equimolar amount of M(dba)2 and [(eta5-Ph2PC5H 4)2Co]+(PF6)- or with M(PPh3)4 and [(eta5-Ph2PC 5H4)2Co]+(PF6) – under similar conditions to afford the dinuclear transition-metal fullerene complexes (eta2-C60)M[(eta 5-Ph2PC5H4)2Co] +(PF6)- (3, M = Pd; 4, M = Pt). In addition, the related complex {[eta5-Ph2P(O)C6H 4]2Co}+(PF6)- (5) was prepared by oxidation of [(eta5-Ph2-PC5H 4)2Co]+(PF6)- with an excess amount of aqueous peracetic acid in acetone at room temperature. While 1-4 are the first examples of neutral and cationic dinuclear M/Ru and M/Co (M = Pd, Pt) fullerene complexes, 5 is the first organocobalt Cp complex containing a phosphoryl substituent. All products 1-5 have been fully characterized by elemental analysis, spectroscopy, and X-ray crystal diffraction techniques and, for 1 and 2, by cyclic voltammetry.

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

Top Picks: new discover of Bis(dibenzylideneacetone)palladium

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Arylation of Adamantanamines: X. Palladium- and Copper-Catalyzed Heteroarylation of Adamantane-Containing Amines with Bromopyridines

The catalytic efficiencies of palladium(0) and copper(I) complexes in the amination of 2-bromopyridine and its fluorine-containing derivatives with (1-adamantyl)methanamine and 2-(1-adamantyloxy)ethanamine were compared. Both types of catalytic systems were shown to be applicable for the preparation of the corresponding N-pyridyl derivatives from 3- and 5-fluoro- and 4-, 5-, and 6-trifluoromethyl-2-bromopyridines. DavePhos was found to be the most efficient ligand in the Pd(0)-catalyzed reactions; however, the reactions with 2-bromo-4-(trifluoromethyl)pyridine and 2-bromo-5-(trifluoromethyl)pyridine were accompanied by formation of a considerable amount of the diarylation product. The diarylation process was significantly suppressed in the presence of copper(I) complexes.

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

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Bidentate ferrocenylphosphines and their palladium(II)dichloride complexes – X-ray structural and NMR spectroscopic investigations and first results of their characteristics in the Pd-catalysed cooligomerisation of 1,3-butadiene with CO2

The chiral 1,1?-bis(di(+)-menthylphosphino)ferrocene (dmenpf, 1b) and achiral 1,1?-bis(diisopropylphosphino)ferrocene (disoppf, 1a) were prepared from the corresponding tertiary chlorophosphines 2b and 2a and the dilithiated ferrocene-TMEDA complex as analytically pure crystals. The synclinic eclipsed conformation of the Cp rings and the Cp(1)-Fe-Cp(1)? angle in 1b was determined to be 175.0(2) by X-ray structure analysis. With H2[PdCl4] 1a forms the bimetallic complex (disoppf)PdCl2 (3a). In contrast to the structure of the free ligand disoppf (1a), the X-ray structure of 3a and the NMR spectra in solution as well as in the solid state show that the P atoms are chemically and magnetically equivalent. The conformation of the Cp rings converts from an eclipsed to a staggered conformation. The ferrocene-based ligands show significant activity in the Pd-catalysed cooligomerisation of 1,3-butadiene with CO2

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

Discovery of Bis(dibenzylideneacetone)palladium

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6-Polyamino-substituted quinolines: Synthesis and multiple metal (CuII, HgII and ZnII) monitoring in aqueous media

Chemoselective palladium-catalyzed arylation of polyamines with 6-bromoquinoline has been explored to prepare chelators for the detection of metal cations in aqueous media. The introduction of a single aromatic moiety into non-protected polyamine molecules was achieved using the commercially available Pd(dba)2/BINAP precatalyst to afford nitrogen chelators, in which the aromatic signalling unit is directly attached to the polyamine residue. Water-soluble receptors were then synthesized using N-alkylation of these polyamines by hydrophilic coordinating residues. By combining rich photophysical properties of the 6-aminoquinoline unit with a high coordination affinity of chelating polyamines and a hydrophilic character of carboxamido-substituted phosphonic acid diesters in a single molecular device, we synthesized chemosensor 5 for selective double-channel (UV-vis and fluorescence spectroscopies) detection of CuII ions in aqueous media at physiological levels. This receptor is suitable for the analysis of drinking water and fabrication of paper test strips for the naked-eye detection of CuII ions under UV-light. By increasing the number of donor sites we also obtained chemosensor 6 which is efficient for the detection of HgII ions. Moreover, chemosensor 6 is also suitable for multiple detection of metal ions because it chelates not only HgII but also CuII and ZnII ions displaying different responses of emission in the presence of these three cations.

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

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Group 10 metal complexes supported by pincer ligands with an olefinic backbone

The coordination chemistry of 2,2?-bis(di-iso-propylphosphino)-trans- stilbene (tPCH-CHP) with group 10 metal centers in a variety of oxidation states is reported; different coordination modes were observed depending on the oxidation state of the metal. With metal centers in the 0 or +1 oxidation state ((tPCH-CHP)Ni, [(tPCH-CHP)Pd]2, (tPCH-CHP)NiCl, (tPCH-CHP)NiI), eta2 coordination of the olefin occurs, whereas, with metals in the +2 oxidation state, C-H activation of the backbone, followed by rapid H-X reductive elimination, was observed, leading to an eta1 coordination of the backbone in (tPC-CHP)MCl (M = Ni, Pd, Pt). Employing the methyl-substituted analogue, 2,2?-bis(di-iso-propylphosphino)-trans- diphenyl-1,2-dimethylethene (tPCMe-CMeP), forced an eta2 coordination of the olefin in [(tPCMe-CMeP)NiCl]2[NiCl4]. The synthesis of the hydride complex (tPC-CHP)NiH was attempted, but, instead, led to the formation of (tPCH-CHP)Ni, indicating that the vinyl form of the backbone can function as a hydrogen acceptor. All metal complexes were characterized by multinuclei NMR spectroscopy, X-ray crystallography, and elemental analysis.

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

Extended knowledge of 32005-36-0

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Preparation of 2-arylated-1,4-phenylenediamines by palladium-catalyzed cross-coupling reactions

Protected 2-iodol-1,4-phenylenediamines were converted to the corresponding magnesium derivative by performing an iodine-magnesium exchange. After transmetalation with zinc bromide, a palladium(0)-catalyzed cross-coupling with various aryl iodides and 5-bromo-2-carbethoxyfuran furnished the expected cross-coupling products in 52-79% yield.

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

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Redox-coupled complexation of 23-phospha-21-thiaporphyrin with group 10 metals: A convenient access to stable core-modified isophlorin-metal complexes

Core-modified isophlorin-metal complexes were successfully prepared by redox-coupled complexation of P,S,N2-hybrid porphyrin with zerovalent palladium, nickel, and platinum. In this transformation, the core-phosphorus atom plays crucial roles in enhancing the electron-accepting ability of the 18pi porphyrin ring and stabilizing the 20pi isophlorin ring owing to high P-M affinity. The isolated Pd and Pt complexes are chemically stable under ambient conditions. The Pd-P,S,N2 isophlorin complex was structurally characterized by X-ray crystallography, which revealed a distorted 20pi plane with a square planar palladium(II) center. Experimental (1H, UV-vis, and X-ray) and theoretical (density functional theory calculations) results suggest that the P,S,N2-isophlorin-metal complexes possess nonaromaticity in terms of both magnetic and geometrical criteria. Copyright

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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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Selective oxidative carbonylation of amines to oxamides and ureas catalyzed by palladium complexes

A new process for converting secondary amines into N,N,N?,N?- tetraalkyloxamides under CO pressure, catalyzed by homogeneous palladium complexes in the presence of 1,4-dichloro-2-butene (DCB) as an oxidant, has been developed. The mechanism of the oxidative double-carbonylation process, consisting of the oxidation of Pd(0) to Pd(11) with DCB through a beta-chloride elimination of the eta3-(chloromethyl) allylpalladiuni(11) intermediate, the formation of mono- and bis(carbamoyl)palladium species, and a reductive elimination of the two carbamoyl ligands, is proposed based on studies of the behavior of carbamoylpalladium complexes. When primary amines are employed with DCB as the oxidant, N,N?-dialkyloxamide is catalytically produced, whereas urea is exclusively produced when iodine is used as the oxidant. The reaction of an N-monopropylcarbamoylpalladium complex with propylamine under CO gave N,N?-dipropylurea, whereas a treatment with diethylamine yielded unsymmetrical N,N-diethyl-N?-propylurea, implying the intermediate formation of propyl isocyanate that is converted into the urea upon a reaction with the added amine. A kinetic study on the reaction of chloro-N- propylcarbamoylpalladium with triethylamine suggested a process proceeding through a base-promoted dcprolonalion of the N-monoalkylcarbamoyl ligand to form propyl isocyanate.

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