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    Borohydride reduction of pyridinium salts. IV. Simultaneous low-temperature formation of (2+2) and (4+2) cycloadducts in the reduction of 1-methyl-4-cyanopyridinium iodide.

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    The redn. of 1-methyl-4-cyano-pyridinium iodide at -45 in 0.8N methanolic NaOH yielded 60% trans-cis-trans-7,8-dicyano-4,11-dimethyl-4,11-diazatricyclo-[6.4.0.02.7] dodeca-5,9-diene (I) contg. only traces of II. Redns. performed at temps. increasing from -45 to -20, yielded ppts. contg. progressively more II, until at > -20 only II was present in the ppt. I was very labile and, in the solid state, at 15-20 was quickly converted to II. If I was rapidly poured into 6N HCl at -45, an insol. product which was sufficiently stable for characterization was immediately formed

    Borohydride reduction of pyridinium salts. V. Thermal dimerization of 1,6-dihydro-1-methylpyridine-2-carbonitrile.

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    The 1,6-dihydropyridine I, obtained by NaBH4 redn. of 2-cyano-1-methylpyridinium iodide, undergoes a thermal dimerization to give the cyclobutane deriv. II. II rearranges, by heating, to the isomeric ethenonaphthyridine III (R = H). Label scrambling observed at 110 in III (R = H) reveals a degenerate thermal [3.3] sigmatropic shift

    pyrroloquinolinequinone : a versatile biological electron carrier

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    The redox properties of the pyrrolo quinoline quinone (PQQ) were studied by means of the specific one-electron reductans NAD dimers, (NAD)2 and (NADP)2. PQQ and (NAD)2 or (NADP)2 give rise to a redox process whose products are pyrrolo quinoline quinol (PQQH2) and coenzymes NAD+ or NADP+. The process implies a two-step one electron transfer via the intermediate pyrrolo quinoline semiquinone radical (PQQ

    ON THE STRUCTURE OF INTERMEDIATE ADDUCTS ARISING FROM DITHIONITE REDUCTION OF PYRIDINIUM SALTS : A NOVEL CLASS OF DERIVATIVES OF THE PARENT SULFINIC ACIDS.

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    13C and 17O NMR spectroscopy show that adducts arising from dithionite reduction of 3- or 3,5-cyano- or carbamoyl-substituted pyridinium salts to the corresponding 1,4-dihydropyridines, are S-anions of esters of the simplest parent sulfinic acid. A pathway for formation of the 1,4- dihydropyridines, involving an intramolecular hydride transfer, is suggested

    Dihydropyridines and pyridones from 3-cyano-1-methylpyridinium iodide in aqueous sodium hydroxide.

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    3-Cyano-1-methylpyridinium iodide added to aq. NaOH and stirred for 2 h gave the isomeric 1,4-, 1,2-, and 1,6-dihydropyridines in the ratio 11:2:1, 5-cyano-1-methyl-2-pyridone, and 3-cyano-1-methyl-2-pyridone which were extd. with CH2Cl2. The aq. layer, after neutralization with H2SO4, gave 2-cyano-glutaconaldehyde Na enolate, shown by NMR to exist in a mesomeric state. The intermediate 2-hydroxydihydropyridines behaved as reducing agents toward the pyridinium cation, involving H- transfer, as well as undergoing the normal ring opening reaction

    Borohydride reduction of pyridinium salts. III.Formation of a Diels-Alder adduct in the reduction of 1-methyl-4-cyanopyridinium iodide.

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    NaBH4 redn. of 1-methyl-4-cyanopyridinium iodide (I) in 1:1 H2O-MeOH gave 1-methyl-4-cyano-1,2,5,6-tetrahydropyridine, whereas similar redn. of I in a 0.8M NaOH-MeOH soln. gave a tricyclododecadiene (II)
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