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


Autoria(s): Mola, 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
Contribuinte(s)

Universitat de Barcelona

Data(s)

28/05/2014

Resumo

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.

Identificador

http://hdl.handle.net/2445/53365

Idioma(s)

eng

Publicador

American Chemical Society

Direitos

(c) American Chemical Society , 2013

info:eu-repo/semantics/openAccess

Palavras-Chave #Síntesi orgànica #Amines #Catalitzadors #Lactames #Nucleòsids #Proves i reactius químics #Organic synthesis #Amines #Catalysts #Lactams #Nucleosides #Chemical tests and reagents
Tipo

info:eu-repo/semantics/article

info:eu-repo/semantics/acceptedVersion