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2013-05-28

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Please use this identifier to cite or link to this item: https://hdl.handle.net/2445/53365

Nucleophile-Catalyzed Additions to Activated Triple Bonds. Protection of Lactams, Imides, and Nucleosides with MocVinyl and Related Groups

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http://dx.doi.org/10.1021/jo4006409

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.

Subject

Síntesi orgànica, Amines, Catalitzadors, Lactames, Nucleòsids, Proves i reactius químics

Subject (English)

Organic synthesis, Amines, Catalysts, Lactams, Nucleosides, Chemical tests and reagents

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Articles publicats en revistes (Química Inorgànica i Orgànica)

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MOLA SOLÀ, Laura, et al. Nucleophile-Catalyzed Additions to Activated Triple Bonds. Protection of Lactams, Imides, and Nucleosides with MocVinyl and Related Groups. Journal of Organic Chemistry. 2013. Vol. 78, num. 12, pags. 5832-5842. ISSN 0022-3263. [consulted: 18 of August of 2026]. Available at: https://hdl.handle.net/2445/53365

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