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Rationale: Although monoketone curcuminoids (MKCs) have been largely investigated due to their biological activities, data on the gas-phase fragmentation reactions of protonated MKCs under collision-induced dissociation (CID) conditions are still scarce. Here, we combined electrospray ionization tandem mass spectrometry (ESI-MS/MS) data, multiple-stage mass spectrometry (MSn), deuterium exchange experiments, accurate-mass data, and thermochemical data estimated by computational chemistry to elucidate and to rationalize the fragmentation pathways of eleven synthetic MKCs. Methods: The MKCs were synthesized by Claisen-Schmidt condensation under basic (1?9) or acidic (10?11) conditions. ESI-CID-MS/MS analyses and deuterium-exchange experiments were carried out on a triple quadrupole mass spectrometer. MSn analyses on an ion trap mass spectrometer helped to elucidate the fragmentation pathways. Accurate-mass data and thermochemical data, obtained at the B3LYP/6?31+G(d,p) level of theory, were used to support the ion structures. Results: The most intense product ions were the benzyl ions ([C7H2R1R2R3R4R5]+) and the acylium ions ([M + H ? C8H3R1R2R3R4R5]+), which originated directly from the precursor ion as a result of two competitive hydrogen rearrangements. Product ions [M + H ? H2O]+ and [M + H ? C6HR1R2R3R4R5]+, which are formed after Nazarov cyclization, were also common to all the analyzed compounds. In addition, ?Br and ?Cl eliminations were diagnostic for the presence of these halogen atoms at the aromatic ring, whereas ?CH3 eliminations were useful to identify the methyl and methoxy groups attached to this same ring. Nazarov cyclization in the gas phase occurred for all the investigated MKCs and did not depend on the presence of the hydroxyl group at the aromatic ring. However, the presence and the position of a hydroxyl group at the aromatic rings played a key role in the Nazarov cyclization mechanism. Conclusions: Our results reinforce some aspects of the fragmentation pathways previously published for 1,5-bis-(2-methoxyphenyl)-1,4-pentadien-3-one and 1,5-bis-(2-hydroxyphenyl)-1,4-pentadien-3-one. The alternative fragmentation mechanism proposed herein can explain the fragmentation of a wider diversity of monoketone curcuminoids.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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The invention discloses a whorl annular phthalazine derivatives, the structural formula of The preparation method is: will be phthalic hydrazide, dinitroso benzylidene acetone in trifluoromethanesulfonic acid as catalyst, acetonitrile as solvent, at a temperature of 20 – 80 C reaction under the condition of 48 hours, column chromatography to obtain whorl annular phthalazine derivatives; the invention provides a simple, efficient, convenient and high efficiency of phthalazine derivatives synthetic method, is to use three trifluoromethane sulfonic acid as catalyst, acetonitrile as the solvent to synthesize whorl annular phthalazine derivatives, has high-efficient, convenient, low cost and the like, application prospect is good. (by machine translation)

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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One-pot synthesis of 3-aza-6,10-diaryl-2-oxa-spiro[4.5]decane-1,4,8-trione from 1,5-diaryl-1,4-pentadien-3-one can be carried out in good yields at 50 C under ultrasound irradiation. This method provided several advantages such as simple work-up procedure, shorter reaction time and higher yield.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Human therapeutic treatment compositions comprise at least two of a curcumin component, a harmine component, and an isovanillin component, and preferably all three in combination. The agents are effective for the treatment of human conditions, especially human cancers.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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The reaction between dibenzyl-ideneacetone (dba) and tri-isopropyl sulfoxonium tetra-fluoro-borate has been reinvestigated. The stereochemistry of the major diasteromeric bis-(gem-dimethyl-cyclo-propane) adduct has now been assigned as [(1RS,3RS)-2,2-dimethyl-3-phenyl-cyclo-prop-yl][(1SR,3SR)-2,2- dimethyl-3-phenyl-cyclo-prop-yl]methanone, C23H26O, by X-ray crystallographic studies on a twinned crystal. The asymmetric unit contains two ml-ecules of the adduct, the conformations of which differ in the orientation of the phenyl ring relative to the adjacent cyclo-propanated double bond. The carbonyl groups of each adduct are aligned approximately along the a axis and in opposite directions to each other. The mol-ecules pack to give a sinusoidal pattern along the b axis. This is the first acyclic bis-(dimethyl-cyclo-prop-yl) ketone for which an X-ray crystal structure determination has been reported, and is also the first bis-cyclo-propanated dba analogue. The knowledge that the major diastereomer has the meso structure (and therefore the confirmation that the minor isomer is the racemate) will prove invaluable in future studies to utilize bis-(dimethyl-cyclo-prop-yl) ketones as reagents, in rearrangement processes, and as potential ligands and ligand precursors in organometallic chemistry.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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The catalytic properties and nature of the nanoparticles forming in the system based on Pd(dba)2 and white phosphorus are reported. A schematic mechanism is suggested for the formation of nanosized palladium-based hydrogenation catalysts. The mechanism includes the formation of palladium nanoclusters via the interaction of Pd(dba)2 with the solvent (N,N-dimethylformamide) and substrate and the formation of palladium phosphide nanoparticles. The inhibiting effect exerted by elemental phosphorus on the catalytic process is due to the conversion of part of the Pd(0) into palladium phosphides, which are inactive in hydrogenation under mild conditions, and the formation of mainly segregated palladium nanoclusters and palladium phosphide nanoparticles. By investigating the interaction between Pd(dba)2 and white phosphorus in benzene, it has been established that the formation of palladium phosphides under mild conditions consists of the following consecutive steps: Pd(0) ? PdP2 ? Pd5P2 ? Pd3P. It is explained why white phosphorus can produce diametrically opposite effects of on the catalytic properties of nanosized palladium-based hydrogenation catalysts, depending on the nature of the palladium precursor.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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The complexes Ru2(CO)6(mu-H)(O=C(CH=CHPh)C(H)=CPh) (5), Ru3(CO)8-(O=C(CH=CHPh)C(H)=CPh)2 (6), and Ru3(CO)7(O=C(CH=CPh)C(H)=CPh)-(O=C(CH2-CH 2Ph)C(H)=CPh) (7) were obtained in the reaction of Ru 3(CO)12 with dibenzylideneacetone PhCH=CHCOCH=CHPh. The structures of complexes 5 and 6 were established by NMR and IR spectroscopy and elemental analysis. The structure of complex 7 was established by X-ray diffraction. The structural and spectroscopic features of the complexes, as well as their possible formation and interconversion pathways are discussed.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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The phosphine-catalyzed annulations between Morita-Baylis-Hillman adduct carbonates and enones are reported. Under the catalysis of PBu3 (20 mol %), cascade [3 + 2] cyclization-allylic alkylation, [2 + 2 + 1] annulation, and [3 + 2] cyclization reactions chemoselectively occur depending on the substituent variation of both the carbonate and enone. These reactions provide efficient syntheses of highly functionalized cyclopentenes and cyclopentanes.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Various 2H-5,6-dihydroselenine derivatives were synthesized by the reaction of alpha-alkoxy carbonylselenoacetamides with alpha,beta-unsaturated ketones in the presence of BF3?Et2O.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Arylation of K2 with Mg(C6F3H2)Br in tetrahydrofuran-dioxane and subsequent addition of either benzonitrile or dibenzylideneacetone (dba) in diethyl ether leads to the formation of labile complexes or respectively.A number of -type complexes have been prepared by addition of the corresponding neutral ligand to chloroform solutions of .Proton, 19F, and 31P n.m.r. data for all the square-planar palladium(II) complexes have been collected and 31P-<1H> spectra show that they are the cis isomers.The complex reacts with NMe4Cl to give 2 and treatment of this with the appropriate alkali-metal salt (KBr, NaI, or KSCN) leads to 2 (X = Br, I, or SCN).The behaviour of the binuclear anions in the solvents acetone and dimethyl sulphoxide has been studied by 19F n.m.r. spectroscopy.The crystal structure of 2<(C6F3H2)2Pd(mu-SCN)(mu-NCS)Pd(C6F3H2)2> has been solved and refined to R = 0.040 based on 3384 observed reflections, confirming the existence of centrosymmetric binuclear anions where the Pd atoms have square-planar co-ordination .

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate