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  • 1
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 1367-1374 
    ISSN: 0887-624X
    Keywords: poly-β-hydroxyalkanoates ; bacterial polyesters ; Pseudomonas oleovorans ; functional polyesters ; reserve polyesters ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly-3-hydroxyalkanoates (PHAs) containing repeating units with terminal alkene substituents at the 3-position were produced by Pseudomonas oleovorans grown with either 7-octeneoic acid [OA(=)] alone, or 10-undeceneoic acid [UND(=)] alone, or mixtures of UND(=) and either nonanoic acid (NA) or octanoic acid (OA). For the latter, the biomass and PHA yields decreased as the fraction of UND(=) increased in the mixed carbon substrates. Essentially all of the repeating units in the PHA obtained from cells grown with UND(=) alone contained terminal alkene groups, including 3-hydroxy-10-undeceneoate, 3-hydroxy-8-noneneoate, and 3-hydroxy-6-hepteneoate units, but less than half of the units in the PHA from OA(=) had alkene substituents. The PHAs obtained from cells grown with various mixtures of UND(=) and either OA or NA were random copolymers, and the fraction of units with alkene substituents in these polymers increased in proportion to the fraction of UND(=) in the mixed carbon substrates. © 1995 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Publication Date: 2018-03-06
    Description: Intramolecular insertion of metal nitrenes into carbon-hydrogen bonds to form -lactam rings has traditionally been hindered by competing isocyanate formation. We report the application of theory and mechanism studies to optimize a class of pentamethylcyclopentadienyl iridium(III) catalysts for suppression of this competing pathway. Modulation of the stereoelectronic properties of the auxiliary bidentate ligands to be more electron-donating was suggested by density functional theory calculations to lower the C–H insertion barrier favoring the desired reaction. These catalysts transform a wide range of 1,4,2-dioxazol-5-ones, carbonylnitrene precursors easily accessible from carboxylic acids, into the corresponding -lactams via sp 3 and sp 2 C–H amidation with exceptional selectivity. The power of this method was further demonstrated by the successful late-stage functionalization of amino acid derivatives and other bioactive molecules.
    Keywords: Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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