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Iridium phosphine abnormal N-heterocyclic carbene complexes in catalytic hydrogen transfer reactions

Several iridium complexes bearing chelating abnormal N-heterocyclic carbenes (NHCs) are shown to be active catalysts for transfer hydrogenation of ketones or enones, dehydrative C-C coupling between primary and secondary alcohols, and dehydrogenation of benzyl alcohol to benzyl benzoate. In the transfer hydrogenation of acetophenone, abnormal NHC complexes give higher activity than a normal analogue. Dehydrative C-C coupling reactions between primary and secondary alcohols result in beta-alkylation of the secondary alcohols, using primary alcohols as the apparent alkylating reagents, and such reactions proceed with high yield and selectivity. These catalytic processes are known to involve metal-mediated temporary borrowing of hydrogen from alcohols and subsequent delivery of the hydrogen to CC and /or CO bonds.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Naphtho[2,3-: B] furan-4,9-dione synthesis via palladium-catalyzed reverse hydrogenolysis

A reverse hydrogenolysis process has been developed for two-site coupling of 2-hydroxy-1,4-naphthoquinones with olefins to produce naphtha[2,3-b]furan-4,9-diones and hydrogen (H2). The reaction is catalyzed by commercially available Pd/C without oxidants and hydrogen acceptors, thereby providing an intrinsically waste-free approach for the synthesis of functionalized and potentially biologically relevant naphtha[2,3-b]furan-4,9-diones.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Chemoselective transfer hydrogenation of Alpha,Beta-unsaturated carbonyls catalyzed by a reusable supported Pd nanoparticles on biomass-derived carbon

We herein report highly chemoselective transfer hydrogenation of alpha,beta-unsaturated carbonyl compounds to saturated carbonyls with formic acid as a hydrogen donor over a stable and recyclable heterogeneous Pd nanoparticles (NPs) on N,O-dual doped hierarchical porous biomass-derived carbon. The synergistic effect between Pd NPs and incorporated heteroatoms on carbon plays a critical role on promoting the reaction efficiency. A series of alpha,beta-aromatic and aliphatic unsaturated carbonyl compounds was selectively reduced to their corresponding saturated carbonyls in up to 97% isolated yields with good tolerance of various functional groups. In addition, the catalyst can be successively reused for at least 6 times without significant loss in reaction efficiency.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Asymmetric double Michael reaction catalyzed by simple primary amine catalysts: A straightforward approach to construct spirocyclic oxindoles

The enantioselective double Michael reaction of N-Boc-3-nonsubstitued oxindoles with dienones catalyzed by chiral monoimide protected cyclohexane-1,2-diamines was developed. A wide range of optically active spirocyclic oxindoles were obtained up to 98% yield and up to 89% ee.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Conversion of bis(o-nitrophenyl)disulfides to heterocycles containing sulfur and nitrogen by the action of samarium diiodide

Treatment of bis(o-nitrophenyl)disulfides 1 with SmI2 led to simultaneous reduction of nitro groups and reductive cleavage of S-S bonds as well as the formation of the active intermediates 2. The intermediates 2 reacted smoothly with aldehydes or ketones, acid chlorides or anhydrides, alpha-bromoketones, and alpha,beta-unsaturated ketones at room temperature to afford the desired benzothiazolines 3, benzothiazoles 4, 2H-1,4-benzothiazines 5, and 2,3-dihydro-1,5-benzothiazepines 6, respectively, in moderate to high yields under mild and neutral conditions.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Electrospray ionization tandem mass spectrometry of monoketone curcuminoids

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£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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A diene-transmissive Diels-Alder reaction involving inverse electron-demand hetero-Diels-Alder cycloaddition of cross-conjugated azatrienes

The initial inverse electron-demand hetero-Diels-Alder reaction of N-sulfonyldivinylmethanimine with electron-rich dienophiles (ethyl vinyl ether and ethyl vinyl sulfide) affords [4+2] cycloadducts with high endo selectivity. The monocycloadducts then undergo a second Diels-Alder reaction on the newly formed diene unit with electron-deficient dienophiles (tetracyanoethylene, 4-phenyl-1,2,4-triazoline-3,5-dione, and N-phenylmaleimide) to give highly stereoselectively the crossed biscycloadducts, hexa- and octahydroquinolines, and octahydropyridopyridazines.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Substituent-Controlled Chemoselective Cleavage of C = C or Csp2 – C(CO) Bond in alpha,beta-Unsaturated Carbonyl Compounds with H-Phosphonates Leading to beta-Ketophosphonates

An unprecedented substituent-controlled chemoselective cleavage of C = C double bond or C(sp2)-C(CO) bond along with aerobic phosphorylation of alpha,beta-unsaturated carbonyl compounds with H-phosphonates through a radical process has been disclosed. The current strategy provides an access to beta-ketophosphonates under mild conditions with a wide substrate scope.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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A convenient synthesis of 1-acyl indolizines by 1,3-dipolar cycloaddition reactions of pyridinium ylides and alpha,beta-unsaturated aldehydes or ketones in the presence of tetrakis-pyridine cobalt dichromate

In the presence of tetrakispyridine cobalt dichromate (CoPy4(HCrO4)2), pyridinium ylides and alpha,beta-unsaturated aldehydes or ketones undergo 1,3-dipolar cycloaddition reactions followed by in situ aromatization to give 1-acyl substituted indolizines in moderate to good yields.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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gamma-Amino butyric acid analogs as novel potent GABA-AT inhibitors: Molecular docking, synthesis, and biological evaluation

A new series, of gamma-amino butyric acid analogs were designed and synthesized as novel potent GABA-AT inhibitors. A structure-activity relationship study was performed by correlating the effect of different substituents with GABA-AT inhibitory activity of the title compounds. The preliminary bioassays showed that acid hydrazones exhibited excellent inhibitory activities in micromolar (0.07-0.56 muM) range, while Schiff’s bases showed variable results. The most potent compound, 4-amino-N’-[(1Z)-1-(2-bromophenyl) ethylidene]butanehydrazide (AHG177) showed inhibitory potency (IC50) of 0.073 muM. Aminobutyrate transaminase is a pyridoxal-P enzyme which follows a bi-bi ping pong mechanism and in pyridoxamine form can readily transaminate only with succinic semialdehyde and 2-oxoglutarate. The results strongly suggest that only the pyridoxal form of the enzyme is capable of reacting with the ligands. Our findings open up the possibility to extend this protocol to different databases in order to find new potential inhibitor for promising targets based on a rational drug design process.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate