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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 502-510 
    ISSN: 0947-6539
    Keywords: alkynes ; C-glycosides ; cobalt complexes ; cyclizations ; enzyme inhibitors ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of gluconolactone 2 with allylmagnesium bromide at low temperatures afforded ketopyranose 3, which could easily be converted into open-chain ketoses (R)-6 and (S)-6. Their reaction with lithioacetylide 9 afforded propargylic alcohol derivatives (R)-10 and (S)-10, which could not be cyclized directly to the desired C-ketosides. They were converted by standard procedures into (R)-14 and (S)-14 and then into dicobalthexacarbonyl complexes (R)-16 and (S)-16. A facile acid-catalyzed ring closure gave the desired C-ketosides (R)-18 α/β and (S)-18α/β, respectively, in different ratios. In order to demonstrate that removal of the protective groups and hydrogenation of the CC triple bond proceed smoothly, (R)-18 α was transformed into the deprotected target molecule (R)-1 α. For the assignment of the new chiral centers at C-2/2′ and at C-8, (S)-18α was transformed into azido derivative (S)-22α, which underwent intramolecular cycloaddition to afford the spiro derivative (S)-25α. Because of the conformational constraints in this molecule, unequivocal configurational assignment was possible with the help of NMR data.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Publication Date: 2022-05-25
    Description: Author Posting. © American Geophysical Union, 2005. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 110 (2005): C05001, doi:10.1029/2004JC002691.
    Description: Numerical simulations of the Hudson River estuary using a terrain-following, three-dimensional model (Regional Ocean Modeling System, ROMS) are compared with an extensive set of timeseries and spatially resolved measurements over a 43-day period with large variations in tidal forcing and river discharge. The model is particularly effective at reproducing the observed temporal variations in both the salinity and current structure, including tidal, spring-neap, and river discharge induced variability. Large observed variations in stratification between neap and spring tides are captured qualitatively and quantitatively by the model. The observed structure and variations of the longitudinal salinity gradient are also well reproduced. The most notable discrepancy between the model and the data is in the vertical salinity structure. While the surface-to-bottom salinity difference is well reproduced, the stratification in the model tends to extend all the way to the water surface, whereas the observations indicate a distinct pycnocline and a surface mixed layer. Because the southern boundary condition is located near the mouth the estuary, the salinity within the domain is particularly sensitive to the specification of salinity at the boundary. A boundary condition for the horizontal salinity gradient, based on the local value of salinity, is developed to incorporate physical processes beyond the open boundary not resolved by the model. Model results are sensitive to the specification of the bottom roughness length and vertical stability functions, insofar as they influence the intensity of vertical mixing. The results only varied slightly between different turbulence closure methods of k-ε, k-ω, and k-kl.
    Description: We gratefully acknowledge support from the U.S. Geological Survey Mendenhall Post-doctoral Research Program for support of J. C. Warner. J. A. Lerczak and W. R. Geyer were supported by the Hudson River Foundation.
    Keywords: Estuary ; Model skill assessment ; Hudson River
    Repository Name: Woods Hole Open Access Server
    Type: Article
    Format: application/pdf
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