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The iodine-catalyzed catalytic formal [3 + 3 + 1] cycloaddition for the preparation of a seven-membered O-heterocyclic ring is presented, which is an achievement of methyl and carbonyl group reactivity of 3-methyl-5-pyrazolones to forge the Csp3-O bond. This novel protocol provides a straightforward and efficient access to structurally diverse fused O-heterocycles through an iodine-catalyzed iodination/Kornblum oxidation/oxidative coupling/C-O bond formation cascade reaction. This approach demonstrates the unprecedented concurrent realization of the unique reactivity among the methyl, methylene, and carbonyl groups in 3-methyl-5-pyrazolones for the construction of 2,3-dihydrooxepine rings. Moreover, a broad substrate scope displays a graceful diversity-oriented synthetic approach.

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Reference:
Benzodioxan,
1,4-Benzodioxane | C8H8O2 – PubChem

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Antihepatotoxic agents include dihydropyrimidinone derivatives with 1,4-benzodioxane. The antihepatotoxic agents are compounds having the structural formula represented by Formula 1: wherein each Z independently represents O, N or S; X represents O or S; R represents aryl, substituted aryl, heteroaryl, or substituted heteroaryl; and pharmaceutically acceptable salts of these compounds.

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Reference:
Benzodioxan,
1,4-Benzodioxane | C8H8O2 – PubChem

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Selective introduction of an iodine atom at the alpha-carbonyl position in various aryl alkyl ketones was effectively achieved by reaction of target molecules with elemental iodine in the presence of N-F reagents. The best results were obtained by using 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetra-fluoroborate) (Selectfluor F-TEDA-BF4) as the iodination mediator and methanol as the solvent. Despite a strongly activated aromatic ring, iodomethyl derivatives were thus exclusively obtained from the corresponding hydroxy and methoxy substituted acetophenone derivatives, 3-acetylindole and 2-acetylbenzofuran, while the alpha-iodo derivative was the main product in the case of iodination of 1,5,6,7-tetrahydro-4H-indol-4-one and 6,7-dihydro-1-benzothiophene-4(5H)-one.

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Reference:
Benzodioxan,
1,4-Benzodioxane | C8H8O2 – PubChem

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Employing simple and readily available aromatic ketones and anilines as starting materials resulted in the construction of 2-acylbenzothiazoles via a novel self-sequence reaction network, which assembles six reactions in one pot. The reaction network not only supplied a novel method for constructing complex molecules but also provided a typical example for logical self-organization synthesis.

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Reference:
Benzodioxan,
1,4-Benzodioxane | C8H8O2 – PubChem

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A rhodium(III)-catalyzed cycloaddition of N-tert-butoxycarbonylhydrazones with internal alkynes was developed. The reaction features a regioselective alpha-imino alkyl C(sp3)?H bond functionalization resulting in selective formation of highly functionalized NH-free pyrroles. Our studies showed that utilizing the N-tert-butoxycarbonyl (N-Boc) as the oxidizing directing group is critical for achieving the observed pyrrole formation versus the isoquinoline formation. To account for the pyrrole formation, we hypothesized that a prior tautomerization of the N-Boc-hydrazones to enamines should occur, followed by regioselective C(sp2)?H cleavage to form a putative five-membered rhodacycle. Subsequent coupling of the rhodacycle with the alkynes would afford the pyrrole products. (Figure presented.).

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Reference:
Benzodioxan,
1,4-Benzodioxane | C8H8O2 – PubChem

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Protein tyrosine phosphatase 1B (PTP1B) is a promising therapeutic target for type 2 diabetes. Herein, we report the evolution of a previously identified 3-phenylpropanoic acid-based PTP1B inhibitor to an orally active lead compound. A series of 3-phenylpropanoic acid-based PTP1B inhibitors were synthesized, and three of them, 3-(4-(9H-carbazol-9-yl)phenyl)-5-(3,5-di-tert-butyl-4- methoxyphenyl)-5-oxopentanoic acid (9), 3-(4-(9H-carbazol-9-yl)phenyl)-5- (4?-bromo-[1,1?-biphenyl]-4-yl)-5-oxopentanoic acid (10) and 3-(4-(9H-carbazol-9-yl)-2-fluorophenyl)-5-(4-cyclohexylphenyl)-5-oxopentanoic acid (16), showed IC50 values at sub-micromolar level. Further in vivo evaluation indicated the sodium salt of 9 not only exhibited significant insulin-sensitizing and hypoglycemia effects, but also decreased the serum levels of triglyceride and total cholesterol in high-fat-diet-induced insulin resistance model mice. Preliminary in vivo pharmacokinetic studies on the sodium salt of 9 revealed its pharmacokinetic profile after oral administration in rats. These results provide proof-of-concept for the dual effects of PTP1B inhibitors on both glucose and lipid metabolisms. A sincere form of flattery: A novel protein tyrosine phosphatase 1B (PTP1B) inhibitor with a 3-phenylpropanoic acid moiety as a phosphotyrosine (pTyr) mimetic was optimized to provide an orally active lead compound with an IC50 value of 0.40 muM against PTP1B and more notably that displayed significant in vivo activity in a murine insulin resistance model.

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Reference:
Benzodioxan,
1,4-Benzodioxane | C8H8O2 – PubChem

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Benzylic alcohols and diarylmethanols with electron-donating substituents in the aromatic ring reacted with aliphatic alcohols in the presence of a catalytic amount of HCl to give the corresponding alkyl arylmethyl ethers. The reactivity of diarylmethanols in the intermolecular dehydration depended on the nature of substituents in the aromatic rings and structure of aliphatic alcohol.

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Reference:
Benzodioxan,
1,4-Benzodioxane | C8H8O2 – PubChem

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Various quinoline-fused 1-benzazepine derivatives were synthesized using the C,N-1,6-bisnucleophile generated in situ from o-aminobenzaldehyde and 2-methylindole through a Mannich-type reaction.

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Reference:
Benzodioxan,
1,4-Benzodioxane | C8H8O2 – PubChem

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An efficient method for constructing 2-acyl-3-aminoindoles from methyl ketones and 2-aminobenzonitriles is described, in which NaHS·nH2O is used as a novel umpolung reagent for the first time in organic synthesis. Mechanistic studies revealed that the key step involved an Eschenmoser sulfide contraction reaction.

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Benzodioxan,
1,4-Benzodioxane | C8H8O2 – PubChem

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The extraction residue from Shengli lignite was sequentially dissolved with cyclohexane, benzene, methanol, ethanol, and isopropanol in an autoclave at 320 C to afford soluble portions (SPs) 1?5 (SP1-SP5) and the final residue (FR). The total yield of SP1-SP5 is ca. 55.1%. FR was subjected to ruthenium ion-catalyzed oxidation and the resulting products were isolated from the reaction mixture and esterified. Both the esterified products and SP1-SP5 were analyzed with a gas chromatograph/mass spectrometer. In total, 342 compounds were identified in SP1-SP5. They can be classified into normal alkanes, branched alkanes, alkenes, alkanedienes, arenes, alkanols, methylcycloalkanes, alkenols, alkylbenzenemethanols, arenols, anisol and substituted anisols, polymethyldihydrobenzofurans, arenofurans, dibenzofurans, ethoxymethylbenzenes, aldehydes, ketones, esters, nitrogen-containing organic compounds, sulfur-containing organic compounds, and other compounds. Among the compounds, arenols are predominant in SP1 and SP2 and the main compounds in SP3, while the main compounds in SP4 and SP5 are esters and arenes, respectively. According to the esterified products identified, the products from FR oxidation can be grouped into non-benzene ring carboxylic acids (NBCAs) and benzenepolycarboxylic acids (BPCAs). The total yield of BPCAs is much higher than that of NBCAs, suggesting that FR is rich in condensed aromatic moieties.

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Reference:
Benzodioxan,
1,4-Benzodioxane | C8H8O2 – PubChem