Malkov, A.V., Stončius, S., Bell, M., Castelluzzo, F., Ramírez-López, P., Biedermannová, L., Langer, V., Rulíšek, L. and Kočovský, P. (2013) Mechanistic dichotomy in the asymmetric allylation of aldehydes with allyltrichlorosilanes catalyzed by chiral pyridine N-oxides. Chemistry: A European Journal, 19(28), pp. 9167-9185. (doi: 10.1002/chem.201203817)
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Publisher's URL: http://dx.doi.org/10.1002/chem.201203817
Abstract
Detailed kinetic and computational investigation of the enantio- and diastereoselective allylation of aldehydes 1 with allyltrichlorosilanes 5, employing the pyridine N-oxides METHOX (9) and QUINOX (10) as chiral organocatalysts, indicate that the reaction can proceed through a dissociative (cationic) or associative (neutral) mechanism: METHOX apparently favors a pentacoordinate cationic transition state, while the less sterically demanding QUINOX is likely to operate via a hexacoordinate neutral complex. In both pathways, only one molecule of the catalyst is involved in the rate- and selectivity-determining step, which is supported by both experimental and computational data.
| Item Type: | Articles |
|---|---|
| Status: | Published |
| Refereed: | Yes |
| Glasgow Author(s) Enlighten ID: | Malkov, Dr Andrei and Kocovsky, Professor Pavel |
| Authors: | Malkov, A.V., Stončius, S., Bell, M., Castelluzzo, F., Ramírez-López, P., Biedermannová, L., Langer, V., Rulíšek, L., and Kočovský, P. |
| College/School: | College of Science and Engineering > School of Chemistry |
| Journal Name: | Chemistry: A European Journal |
| Journal Abbr.: | Chem. Eur J. |
| ISSN: | 0947-6539 |
| ISSN (Online): | 1521-3765 |
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