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- Title
NMR and DFT Study of the Copper(I)-Catalyzed Cycloaddition Reaction: H/D Scrambling of Alkynes and Variable Reaction Order of the Catalyst.
- Authors
Kalvet, Indrek; Tammiku‐Taul, Jaana; Mäeorg, Uno; Tämm, Kaido; Burk, Peeter; Sikk, Lauri
- Abstract
Mechanism of an efficient and easily applicable catalytic system for the copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction, consisting of phosphane-ligated CuI carboxylates and apolar/aprotic solvent was investigated by means of 1H NMR reaction monitoring techniques, isotope exchange studies, and DFT calculations (at the M06L/6-311++G(d,p)//B97D/cc-pVDZ (SDD) level of theory). Kinetic analysis indicates 1st order kinetics with respect to [Azide] and nonlinear positive order in [Cu]. H/D scrambling between alkynes reveals a quickly reached equilibrium existing between CuI-carboxylates and CuI-acetylides and that proton transfer processes are mediated by acetate/acetic acid system. According to the computational results, the Cu-triazolide forms a dinuclear structure that equalizes the copper atoms in the catalytic complex.
- Subjects
ALKYNES; RING formation (Chemistry); COPPER catalysts; NUCLEAR magnetic resonance; DENSITY functional theory; CHEMICAL kinetics
- Publication
ChemCatChem, 2016, Vol 8, Issue 10, p1804
- ISSN
1867-3880
- Publication type
Article
- DOI
10.1002/cctc.201600176