Organic & Biomolecular Chemistry · 2005 · 101 citations · 23 references
Natural SciencesChemistryAnalytical ChemistryChemical KineticsOrganic ChemistryChemical Reaction KineticsChemical ReactionsHeterocyclic ChemistryKinetic Isotope EffectsOrganic SynthesisSubstitution ReactionsDeuterium Isotope EffectHammett AnalysisKinetic Isotope Effect AnalysisKinetic Isotope Effect In Organic ReactionsPrimary Kinetic Isotope EffectRadical MechanismsRadical Substitution ReactionsSolvent Kinetic Isotope Effect
TMSN3 and PhI(OAc)2 were found to promote high-yield azide substitution of ethers, aldehydes and benzal acetals. The reaction is fast and occurs at zero to ambient temperature in acetonitrile. However, it is essential for the reaction that TMSN3 is added subsequent to the mixture of PhI(OAc)2 and the substrate. A primary deuterium kinetic isotope effect was found for the azidonation of benzyl ethers both with TMSN3-PhI(OAc)2 and with IN3. Also a Hammett free energy relationship study of this reaction showed good correlation with sigma+ constants giving with rho-values of -0.47 for TMSN3-PhI(OAc)2 and -0.39 for IN3. On this basis a radical mechanism of the reaction was proposed.
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Yasuyuki Kita, Hirofumi Tohma, Kenji HATANAKA et al. · Journal of the American Chemical Society · 1994 · 447 citations
Philip Magnus, Jérôme Lacour, P. Andrew Evans et al. · Journal of the American Chemical Society · 1996 · 156 citations
Total synthesis of the ionophore antibiotic CP-61,405 (routiennocin)
Nikesh R. Kotecha, Steven V. Ley, Sergio Mantegani et al. · Tetrahedron · 1992 · 101 citations