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Title: Nucleophile-Catalyzed Additions to Activated Triple Bonds. Protection of Lactams, Imides, and Nucleosides with MocVinyl and Related Groups
Author: Mola Solà, Laura
Font, Joan
Bosch Hereu, Lluís
Caner, Joaquim
Costa i Arnau, Anna M.
Etxebarría-Jardí, Gorka
Pineda, Oriol
Vicente, David D.
Vilarrasa i Llorens, Jaume
Keywords: Síntesi orgànica
Proves i reactius químics
Organic synthesis
Chemical tests and reagents
Issue Date: 28-May-2013
Publisher: American Chemical Society
Abstract: Additions of lactams, imides, (S)-4-benzyl-1,3-oxazolidin-2-one, 2-pyridone, pyrimidine-2,4-diones (AZT derivatives), or inosines to the electron-deficient triple bonds of methyl propynoate, tert-butyl propynoate, 3-butyn-2-one, N-propynoylmorpholine, or N-methoxy-N-methylpropynamide in the presence of many potential catalysts were examined. DABCO and, second, DMAP appeared to be the best (highest reaction rates and E/Z ratios), while RuCl3, RuClCp*(PPh3)2, AuCl, AuCl(PPh3), CuI, and Cu2(OTf)2 were incapable of catalyzing such additions. The groups incorporated (for example, the 2-(methoxycarbonyl)ethenyl group that we name MocVinyl) serve as protecting groups for the above-mentioned heterocyclic CONH or CONHCO moieties. Deprotections were accomplished via exchange with good nucleophiles: the 1-dodecanethiolate anion turned out to be the most general and efficient reagent, but in some particular cases other nucleophiles also worked (e.g., MocVinyl-inosines can be cleaved with succinimide anion). Some structural and mechanistic details have been accounted for with the help of DFT and MP2 calculations.
Note: Versió postprint del document publicat a:
It is part of: Journal of Organic Chemistry, 2013, vol. 78, num. 12, p. 5832-5842
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ISSN: 0022-3263
Appears in Collections:Articles publicats en revistes (Química Inorgànica i Orgànica)

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