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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 Amines Catalitzadors Lactames Nucleòsids Proves i reactius químics Organic synthesis Amines Catalysts Lactams Nucleosides 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: http://dx.doi.org/10.1021/jo4006409 |
It is part of: | Journal of Organic Chemistry, 2013, vol. 78, num. 12, p. 5832-5842 |
URI: | http://hdl.handle.net/2445/53365 |
Related resource: | http://dx.doi.org/10.1021/jo4006409 |
ISSN: | 0022-3263 |
Appears in Collections: | Articles publicats en revistes (Química Inorgànica i Orgànica) |
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