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Late-stage functionalization of 1,2-dihydro-1,2-azaborines via regioselective iridium-catalyzed C-H borylation: The development of a new N,N-bidentate ligand scaffold

The first general late-stage functionalization of monocyclic 1,2-azaborines at the C(6) position is described. Ir-catalyzed C-H borylation occurs regioselectively at the C(6) position of B-substituted 1,2-azaborines and is compatible with a range of substitution patterns at boron (e.g., hydride, alkoxide, alkyl, and aryl substituents). Subsequent Suzuki cross coupling with aryl- and heteroaryl bromides furnishes 1,2-azaborine-based biaryl compounds including 6-[pyrid-2-yl]-1,2-azaborines that represent novel kappa2-N,N-bidentate ligands. The 6-[pyrid-2-yl]-B-Me-1,2-azaborine ligand has been demonstrated to form an emissive coordination complex with dimesitylboron that exhibits bathochromically shifted absorption and emission maxima and a higher photoluminescence quantum yield compared to its carbonaceous analogue.

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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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Platinum(II), palladium(II), and nickel(II) thiosalicylate complexes

A series of platinum(II), palladium(II) and nickel(II) complexes containing thiosalicylate ligands have been prepared by the reaction of [MX2L2] complexes [X = halide or acetate; L or L2 = ancillary neutral donor ligand such as a tertiary phosphine or cycloocta-1,5-diene (cod)] with thiosalicylic acid in methanol with added pyridine. Displacement of the cod ligand from [Pt(SC6H4CO2)(cod)] with phosphines and phosphites allows the synthesis of additional derivatives. The complexes [Pt(SC6H4CO2)(PPh3)2] and [Ni(SC6H4CO2)(dppp)] [dppp = 1,3-bis(diphenylphosphino)propane] have been the subjects of single-crystal X-ray diffraction studies. While both complexes contain the expected approximately square-planar metal co-ordination environments, the plane of the thiosalicylate ligand is inclined at an angle of 45.9 to the platinum co-ordination plane, but at only 9.4 to the nickel plane. The results of an electrospray mass spectrometry study of the thiosalicylate complexes and some related thioglycolate, 2-sulfanylpropionate and salicylate derivatives are discussed in terms of the stabilities of the 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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3-Boryl-2,1-borazaronaphthalene: Umpolung Reagents for Diversifying Naphthalene Isosteres

A Pd-catalyzed Miyaura borylation of 3-bromo-2,1-borazaronaphthalenes is reported. This method allows the formation of umpolung reagents for subsequent Pd-mediated cross-coupling. Coupling of this nucleophilic partner with a variety of commercially available aryl- and heteroaryl halides allows facile and rapid diversification of these cores.

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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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Novel hetero-bimetallic metalla-macrocycles based on the bis-1-pyridyl ferrocene (see abstract)

The bidentate sandwich ligand [Fe(eta5-C5H4-1-C5H 4N)2] has been prepared, structurally characterized and employed in the preparation of the novel supramolecular heterobimetallic metalla-macrocycles [Fe(eta5-C5H4-1-C5H 4N)2]- Ag2(NO3)2¡¤1.5H2O, [Fe(eta5-C5H4-1-C5H 4N)2]Cu2-(CH3COO)4 ¡¤3H2O and [Fe(eta5-C5H4-1-C5H4 N)2]Zn2Cl4.

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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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Discovery of beta-Arrestin Biased Ligands of 5-HT7R

Though many studies have been published about therapeutic potentials of selective 5-HT7R ligands, there have been few biased ligands of 5-HT7R. The development of potent and selective biased ligands of 5-HT7R would be of great help in understanding the relationship between pharmacological effects and G protein/beta-arrestin signaling pathways of 5-HT7R. In order to identify 5-HT7R ligands with biased agonism, we designed and synthesized a series of tetrahydroazepine derivatives 1 and 2 with arylpyrazolo moiety or arylisoxazolo moiety. Through several biological evaluations such as binding affinity, selectivity profile, and functions in G protein and beta-arrestin signaling pathways, 3-(4-chlorophenyl)-1,4,5,6,7,8-hexahydropyrazolo[3,4-d]azepine 1g was discovered as the beta-arrestin biased ligand of 5-HT7R. In an electroencephalogram (EEG) test, 1g increased total non-rapid eye movement (NREM) sleep time and decreased total rapid eye movement (REM) sleep time.

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

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Synthesis of 3-trifluoromethylbenzo[ b ]furans from phenols via direct ortho functionalization by extended pummerer reaction

A concise and diversity-oriented route to trifluoromethylbenzo[b]furans has been devised. A variety of phenols are directly converted to the corresponding 2-methylthio-3-trifluoromethylbenzo[b]furans by new triflic-anhydride-mediated extended Pummerer annulation reactions with trifluoromethylketene dithioacetal monoxide. The methylthio group of the products undergoes further transformations, which increase the diversity of available trifluoromethylbenzo[b]furans.

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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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Luminescent infinite coordination polymer materials from metal-terpyridine ligation

A new class of infinite coordination polymers (CP) was synthesized using a tetrahedral tetrakis[4-(4?-phenyl-2,2?:6?,2??- terpyridine)phenyl]methane ligand as an organic node to direct the three-dimensional growth of the network and MII (M = Zn, Fe, Ni, and Ru) ions as inorganic linkers, an approach that is the opposite of the metal-as-a-node strategy used in the construction of metal-organic frameworks (MOFs). The unusual rod-like morphology of the resulting microporous materials can be tuned via solvents and reaction conditions. The covalent entrapment of a [Ru(tpy)2]2+ moiety in the skeleton of the 3D-network enables the Ru-CP to exhibit room-temperature luminescence.

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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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Isolation and structural characterization of some stable Pd(II) carboxylate complexes supported by 1,1?-bis(diphenylphosphino) ferrocene (dppf)

Although catalytically active palladium phosphine carboxylates are generally unstable, a series of such complexes are stabilized by dppf, viz. Pd(O2CR)2(dppf) [R = CF3I, CF2CF3 II [1,43] CF2CF2CF3 III, CHCl2 IV, o-C6H4Cl VI, CH2CO2H VII, CH=CHCO2H VIII]. They have been spectroscopically characterized and their structures determined by X-ray single-crystal crystallography. Two derivatives viz. Pd(O4C2-O,O?)(dppf) IX and PdCl(O2CPh)(dppf) X are included for comparison. They are invariably mononuclear with chelating phosphine and unidentate carboxylates. The more labile (and less basic) carboxylates tend to form complexes that are more resistive to reductive decomposition. Pd(O2CPh)2(dppf) V decomposes readily to PdCl2(dppf) in the presence of chlorinated solvents.

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

Properties and Exciting Facts About 1,1′-Bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex

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Identification of Pyridinium with Three Indole Moieties as an Antimicrobial Agent

A novel pyridinium with three indole moieties, tricepyridinium, was obtained from the culture of an Escherichia coli clone incorporating metagenomic libraries from the marine sponge Discodermia calyx. For the important structural elements of tricepyridinium to be investigated for antibacterial activity, tricepyridinium and its analogues were chemically synthesized. Tricepyridinium had antimicrobial activity, but not against E. coli, and cytotoxicity against P388 cells. Additional bioassays with its synthetic analogues revealed that the intriguing combination of the indole moieties, most likely derived from three tryptamines, as well as the pyridinium moiety were chiefly responsible for its potent biological activities.

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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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METHOD FOR DEUTERATION OR TRITIATION OF HETEROCYCLIC RING

The present invention relates to a method for deuteration of a heterocyclic ring, which comprises subjecting a compound having a heterocyclic ring to sealed refluxing state in a deuterated solvent in the presence of an activated catalyst selected form a palladium catalyst, a platinum catalyst, a rhodium catalyst, a ruthenium catalyst, a nickel catalyst and a cobalt catalyst. In accordance with a method of the present invention, a hydrogen atom belonging to a heterocyclic ring of a compound having a heterocyclic ring can be very efficiently deuterated because temperature of deuteration reaction can be maintained at higher than boiling point of the solvent.Further, a method for deuteration of the present invention can be applied widely to deuteration of various compounds having a heterocyclic ring which are liable to decomposition under supercritical conditions or acidic conditions, leading to industrial and efficient deuteration of a compound having a heterocyclic ring.

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