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Synthetic applications of samarium(II) iodide mediated regioselective cleavage of phenylsulfonyl activated cyclopropyl ketones

Reductive cleavage of phenylsulfonyl activated cyclopropyl ketones with samarium(II) iodide led regioselectively to samarium enolates or dienolates. These were trapped with some alkylating agents.

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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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Synthesis of pyridine-dicarboxamide-cyclohexanone derivatives: Anticancer and alpha-glucosidase inhibitory activities and in silico study

An efficient and practical method for the synthesis of 2,6-diaryl-4-oxo-N,N0-di(pyridin-2 -yl)cyclohexane-1,1-dicarboxamide is described in this present study, which occurs through a double Michael addition reaction between diamide and various dibenzalacetones. The reaction was carried out in dichloromethane (DCM) in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). The anticancer activities of the synthesized compounds were evaluated in several cancer cell lines, including MCF-7, MDA-MB-231, SAS, PC-3, HCT-116, HuH-7 and HepG2 cells. From these experiments, we determined that MDA-MB-231 was the most sensitive cancer cell line to the compounds 3c, 3e, 3d, 3j and 3l, which exhibited variable anticancer activities (3l [IC50 = 5 ± 0.25 muM] > 3e [IC50 = 5 ± 0.5 muM] > 3c [IC50 = 7 ± 1.12 muM] > 3d [IC50 = 18 ± 0.87 muM] > 3j [IC50 = 45 ± 3 muM]). Of these, 3l (substituted p-trifluoromethylphenyl and chloropyridine) showed good potency (IC50 = 6 ± 0.78 muM) against HCT-116 colorectal cancer cells and exhibited high toxicity against HuH-7 liver cancer cells (IC50 = 4.5 ± 0.3 muM). These values were three times higher than the values reported for cisplatin (IC50 of 8 ± 0.76 and 14.7 ± 0.5 muM against HCT-116 and HuH-7 cells, respectively). The highest a-glucosidase inhibitory activity was detected for the 3d, 3i and 3j compounds. The details of the binding mode of the active compounds were clarified by molecular docking studies.

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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

Something interesting about C17H14O

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Reaction of Ru3(CO)12 with dibenzylideneacetone

The thermal reaction of Ru3(CO)12 with dibenzylideneacetone PhCH=CHCOCH=CHPh (1) was studied. From the solution, the trinuclear complexes Ru3(CO)6{mu3- eta2-eta2-eta2-O=C(CH= CHPh)-CH=CPh} 2 (6) and Ru3(CO)7{eta2-O=C(CH= CHPh)CH=CPh}{mu-eta-eta4-O-C(CH=CHPh)-CH-CPh-CH(CH 2Ph)C(O)(CH=CHPh)}{mu3-eta-eta-eta4- (CH2Ph)CH=C(O)-CH=CHPh} (7) were isolated, and the precipitate was found to contain the tetranuclear complex Ru4(CO)8{mu 3-eta-eta2-eta6-O-C(CH=CHPh)= CH-CPh-CH(CH2Ph)-C(O)-CH=CHPh}2 (8). The organic ligand in complexes realizes different coordination modes forming five-membered oxaruthenacycle, eta3-coordinated dihydropyran cycle, eta4-coordinated diene, or oxadiene fragments. Complex 7 is unstable and undergoes chemical transformations yielding complex 8. Reversible changes occur with complex 8 upon dissolution in acetone, and binuclear complex Ru2(CO)4(eta-O= CMe2)(mu-eta2- eta6-O-C(CH=CHPh)=CH-CPh-CH(CH2Ph)-C(O)-CH=CHPh) (9) is formed. The central Ru2O2 cycle in complex 8 is cleaved and the formed vacant coordination site is occupied by an acetone molecule in complex 9. Complexes 6-9 were characterized by IR and 1H NMR spectroscopy, and their structures were determined by single-crystal X-ray diffraction analysis. The structural and spectroscopic features and possible pathways of the complexes’ transformations 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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Efficient michael addition of indoles using bismuthyl perchlorate as catalyst

An efficient method for Michael addition of indoles hasbeen developed using bismuthyl perchlorate (BiOClO4·xH2O) as catalyst. The reaction proceeds to give 3-substituted indoles excellently stirring indoles and Michael acceptors in acetonitrile in the presence of the catalyst at room temperature or in much shorter reaction times under sonication at ambient temperature.{A figure is presented}.

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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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REACTIONS OF 4,5-DIAMINO-3-METHYL-1-PHENYLPYRAZOLE WITH DIARYLIDENEACETONES

The reaction of 4,5-diamino-3-methyl-1-phenylpyrazole with dibenzylideneacetone and its 4,4′-derivatives has been studied; the reactions lead to aromatic 1H-2,3-dihydropyrazolo<5,4-b>-1,5-diazepine derivatives.The reaction pathway has also been identified.

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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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Catalytic enantioselective one-pot aminoborylation of aldehydes: A strategy for construction of nonracemic alpha-amino boronates

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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Chemoselective Hydrogenation of alpha,beta-Unsaturated Carbonyls Catalyzed by Biomass-Derived Cobalt Nanoparticles in Water

Herein, we report highly chemoselective hydrogenation of alpha,beta-unsaturated carbonyls to saturated carbonyls catalyzed by cobalt nanoparticles supported on the biomass-derived carbon from bamboo shoots with molecular hydrogen in water, which is the first prototype using a heterogeneous non-noble metal catalyst for such organic transformation as far as we know. The optimal cobalt nanocatalyst, CoOx@NC-800, manifested remarkable activity and selectivity for hydrogenation of C=C in alpha,beta-unsaturated carbonyls under mild conditions. A broad set of alpha,beta-aromatic and aliphatic unsaturated carbonyls were selectively reduced to their corresponding saturated carbonyls in up to 99 % yields with good tolerance of various functional groups. Meanwhile, a new straightforward one-pot cascade synthesis of saturated carbonyls was realized with high activity and selectivity via the cross-aldol condensation of ketones with aldehydes followed by selective hydrogenation. More importantly, this one-pot strategy is applicable for the expedient synthesis of Loureirin A, a versatile bioactive and medicinal molecule, from readily available starting materials, further highlighting the practical utility of the catalyst. In addition, the catalyst can be easily separated for successive reuses without significant loss in both activity and selectivity.

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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 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:
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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Phosphazene base-catalyzed double michael addition: Stereoselective synthesis of cyclohexanones

Phosphazene bases have been utilized as efficient organocatalysts to catalyze the double Michael additions of divinyl ketones with active methylenes to afford functionalized cyclohexanones in 36-91% yields with >25:1 diastereoselectivity.

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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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FeCl3-catalyzed formation of indolizine derivatives via the 1,3-dipolar cycloaddition reaction between azomethine ylides and chalcones or dibenzylideneacetones

The FeCl3-catalyzed 1,3-dipolar cycloaddition reaction of pyridinium-1-yl(quinolin-2-yl)methanide, prepared in situ from the iodine catalyzed reaction of 2-methylquinoline and pyridine in the presence of base, with chalcones or dibenzylideneacetones, in the one-pot synthesis of aryl(2-aryl-3-(quinolin-2-yl)indolizin-1-yl)methanones is described.

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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