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Barbituric acid 2 upon Michael addition with dibenzal acetones 1a-c afforded the corresponding diazaspiro derivatives 3a-c. The base-catalyzed condensation of 3a-c with various aromatic aldehydes produces diarylidine derivatives 4a-l. The diarylidene compounds 4a-l on condensation with hydrazine, phenyl hydrazine, hydroxylamine, urea, guanidine carbonate, and hydrazine hydrate with acetic acid afforded their respective in situ oxidized products 5, 6, 7, 8, 9, and 10. The structures of the compounds are ascertained from their analytical and spectral data. Some of the compounds are screened for their biological activities against E. coli, B. cirroflagellosus, A. niger, and C. albicans.

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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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N-Acetonylazoles react with chalcones in the presence of a base to give trans-3,5-disubstituted 6-(N-azolyl)cyclohex-2-enones. Usually, the reactions are fast and high-yielding.

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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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(Chemical Equation Presented) The synthesis of monodisperse oligo(p-phenyleneethynylene)s 8an with alternating 2,5-dihexyl-1,4-phenylene and 6,14-di-tert-butyl-1,4-triptycylene units and orthogonally protected alkyne end groups is reported. Starting from 6,14-di-tert-butyl-1-(2-triisopropylsilylethynyl)-4-(2-trimethylsilylethynyl) -triptycene (5a), 1,4-dihexyl-2,5-diiodobenzene (10), and 1,4-dihexyl-2-iodo-5- (3-hydroxyprop-1-ynyl)-benzene (9), oligomers with up to four repeating units, i.e., eight phenyleneethynylene units, were prepared through a partially divergent-convergent route with the alkynyl-aryl (Sonogashira-Hagihara) coupling as the key reaction. The starting compound 5a was prepared from triptycenequinone through a sequence of addition of 2- trialkylsilylethynyllithium, reduction and concomitant elimination of water, conversion of the phenol into a triflate, and finally Pd/Cu-catalyzed coupling with trialkylsilylethyne. A similar access to the key compound for a stringent divergent-convergent route, 6,14-di-tert-butyl-1-(3-hydroxybut-1-ynyl)-4-(2- triisopropylsilylethynyl)triptycene (6), is reported. The optical properties of the oligomers 8an and the corresponding oligo(2,5-dihexyl-1,4- phenyleneethynylene) s in dilute solution are almost identical, whereas they differ significantly for the solid, undiluted compounds.

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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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We report a strategy for the conversion of aldehydes to enantiomerically enriched alpha-amino boronates through the intermediacy of in situ-generated silylimines. This transformation is brought about by Pt-catalyzed asymmetric addition of B2(pin)2 across the imine double bond. An attractive feature of the intermediate diboration adduct is that it can be acylated directly and provides convenient access to important N-acyl alpha-amino boronic ester derivatives.

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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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A zirconium borohydride piperazine complex (Ppyz)Zr(BH4) 2Cl2, obtained by the reaction of an ethereal solution of ZrCl4 and LiBH4 with piperazine is a stable, selective and efficient reducing agent. (Ppyz)Zr(BH4)2Cl 2 reduces aldehydes, ketones, silylethers, alpha, beta-unsaturated carbonyl compounds and esters. The reactions were performed in diethyl ether at room temperature or under reflux, and the yields of the corresponding alcohols were excellent. The selective reduction of aldehydes in the presence of ketones and complete regioselectivity in the reduction of alpha,beta-unsaturated carbonyl groups were observed.

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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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1,5-Diphenylpenta-1,4-dien-3-ones (4) are cyclometalated with benzylpentacarbonylmanganese to form [[1-phenyl-2-((E)-3-phenylprop-2-en-1-oyl-kappaO)]ethenyl-kappaC 1]tetracarbonylmanganese derivatives (5). Coupling of 5 with alkynes in some cases gives [4-phenyl-2-(2-phenylethenyl)pyranyl-eta5]tricarbonylmanganese complexes (6) analogous to those previously reported for beta-manganated chalcones, but in other cases an alternative cyclisation pathway subsequent to insertion of alkyne into the C-Mn bond leads to [6-oxo-4,7-diphenylcyclohepta-1,4-dienyl-1,2,3,4,5-eta]tricarbonylmanganese complexes (7). The X-ray crystal structure determination is reported for one such compound, [6-oxo-2,4,7-triphenylcyclohepta-1,4-dienyl-1,2,3,4,5-eta]tricarbonylmanganese (7a), derived from 1,5-diphenylpenta-1,4-dien-3-one and phenylacetylene. The 7-phenyl group is found to occupy the endo position, and a mechanism involving Mn-mediated aryl migration is suggested to explain this stereochemistry. The reaction of 7a with ammonium cerium(IV) nitrate gives a low yield of 2-nitro-3,5,7-triphenylcyclohepta-2,4,6-trien-1-one (9), whose structure was established by X-ray crystal structure analysis. The pyranyl complexes (6) provide the corresponding pyrylium triiodide salts (8) when demetalated with iodine.

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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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Both ferrocenethiol and ferrocene-1,1′-dithiol, Fe(C5H5)(C5H4SH) and Fe(C5H4SH)2, add to activated olefins to give 1:1 and 1:2 adducts, respectively.The base-catalysed (NEt3) reactions of the monofunctional ferrocenethiol with the mono-olefins methyl methacrylate, methyl vinyl sulfone and benzylidene acetone lead to expected 1:1 adducts whereas 2:1 adducts are obtained with bifunctional olefins such as divinyl sulfone and dibenzylidene acetone.The corresponding bifunctional ferrocene-1,1′-dithiol gives 1:2 adducts with methyl methacrylate, methyl vinyl ketone and benzylidene acetone.For comparison, the aliphatic 2-ferrocenyl-ethanethiol, Fe(C5H5)(C5H4-CH2CH2SH), was reacted with methyl vinyl sulfone and divinyl sulfone.In all cases, the disulfides Fc-SS-Fc and Fc-CH2CH2-SS-CH2CH2-Fc, respectively, are also formed.The acid-catalysed (HCl) reactions of ferrocenethiol and ferrocene-1,1′-dithiol, Fe(C5H5)(C5H4SH) and Fe(C5H4SH)2, with isobutyl vinyl ether produce the expected 1:1 and 1:2 adducts although the formation of dimercaptals is also possible.Thus the reaction of ferrocene-1,1′-dithiol with isobutyl vinyl ether leads to both the 1:2 adduct and the 2-methyl 1,3-dithia-<3>ferrocenophane, Fe(C5H4S)2CH(CH3), and the HCl-catalysed addition of ferrocenethiol to 1,4-butadienol divinyl ether gives 1,1-di(ferrocenylmercapto) ethane, CH3CH(SFc)2.The new sulfur derivatives of ferrocene were characterized by 1H and 13C NMR spectroscopy.Keywords: Iron; Ferrocene; Ferrocene thiol; Addition to olefins; NMR

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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 Pt-catalyzed enantioselective diboration of terminal alkenes can be accomplished in an enantioselective fashion in the presence of chiral phosphonite ligands. Optimal procedures and the substrate scope of this transformation are fully investigated. Reaction progress kinetic analysis and kinetic isotope effects suggest that the stereodefining step in the catalytic cycle is olefin migratory insertion into a Pt-B bond. Density functional theory analysis, combined with other experimental data, suggests that the insertion reaction positions platinum at the internal carbon of the substrate. A stereochemical model for this reaction is advanced that is in line both with these features and with the crystal structure of a Pt-ligand complex.

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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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2,5-Cyclohexadienyl-substituted aryl or vinylic iodides have been reacted with carbon nucleophiles (diethyl malonate and 2-methyl-1,3- cyclohexanedione), nitrogen nucleophiles (morpholine, potassium phthalimide, N-benzyl tosylamide, di-tert-butyl iminodicarboxylate, lithium azide, and anilines), a sulfur nucleophile (sodium benzenesulfinate), and oxygen nucleophiles (lithium acetate and phenols) to afford products of cyclization and subsequent cross-coupling in good to excellent yields. In most cases, this process is highly diastereoselective. The reaction is believed to proceed via (1) oxidative addition of the aryl or vinylic iodide to Pd(0), (2) organopalladium addition to one of the carbon-carbon double bonds, (3) palladium migration along the carbon chain on the same face of the ring to form a pi-allylpalladium intermediate, and (4) nucleophilic displacement of the palladium.

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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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Tandem anionic oxy-Cope rearrangement/radical oxygenation reactions provide delta,?-unsaturated alpha-(aminoxy) carbonyl compounds, which serve as convenient precursors to diverse compound classes. Functionalized carbocycles are accessible by very rare all-carbon 5-endo-trig cyclizations, but also common 5-exo-trig radical cyclizations, based on the persistent radical effect. The tandem reactions can be further extended by highly diastereoselective allylation or reduction steps to give complex scaffolds.

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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