Metal Free Azide–Alkyne Click Reaction: Role of Substituents and Heavy Atom Tunneling
| Autor: | Ayan Datta, Sharmistha Karmakar |
|---|---|
| Rok vydání: | 2015 |
| Předmět: |
Models
Molecular chemistry.chemical_classification Azides Temperature Alkyne Photochemistry Cycloaddition Surfaces Coatings and Films Ring strain chemistry.chemical_compound Models Chemical chemistry Alkynes Intramolecular force Kinetic isotope effect Materials Chemistry Click chemistry Quantum Theory Click Chemistry Azide Physical and Theoretical Chemistry Methyl azide |
| Zdroj: | The Journal of Physical Chemistry B. 119:11540-11547 |
| ISSN: | 1520-5207 1520-6106 |
| Popis: | Metal free click reactions provide an excellent noninvasive tool to modify and understand the processes in biological systems. Release of ring strain in cyclooctynes on reaction with azides on the formation of triazoles results in small activation energies for various intermolecular Huisgen reactions (1-9). Substitution of difluoro groups at the α, α' position of the cyclooctyne ring enhances the rates of cycloadditions by 10 and 20 times for methyl azide and benzyl azide respectively at room temperature. The computed rate enhancement on difluoro substitution using direct dynamical calculations using the canonical variational transition state theory (CVT/CAG) with small curvature tunneling (SCT) corrections are in excellent agreement with the experimental results. For the intramolecular click reaction (10) notwithstanding its much higher activation energy, quantum mechanical tunneling (QMT) enhances the rate of cycloaddition significantly and increases the N(14)/N(15) primary kinetic isotope effect at 298 K. QMT is shown to be rather efficient in 10 due to a thin barrier of ∼2.4 Å. The present study shows that tunneling effects can be significant for intramolecular click reactions. |
| Databáze: | OpenAIRE |
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