Réactions d'addition nucleophile sur les cétones. Influence de l'environnement stérique sur la position de l'état de transition
✍ Scribed by B. Boyer; G. Lamaty; C. Moreau
- Publisher
- Elsevier Science
- Year
- 2010
- Tongue
- English
- Weight
- 283 KB
- Volume
- 100
- Category
- Article
- ISSN
- 0165-0513
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✦ Synopsis
In the present investigation, we have measured the secondary kinetic deuterium isotope effects in hydroxylamine addition reaction for a series of cyclohexanones, both hindered and unhindered. We observed a slightly direct isotope effect, k^H^/k^D^ > 1.00, for unhindered cyclohexanones and an inverse isotope effect, k^H^/k^D^ < 1.00, for hindered cyclohexanones; this inversion of the isotope effects is attributed to a decrease of the torsional strain through the intervention of an “effet stérique de compression” that induce a slight deformation of the cycle and changes the angle of approach of the nucleophile.
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