Mechanistic dichotomy in the asymmetric allylation of aldehydes with allyltrichlorosilanes catalyzed by chiral pyridine N-oxides

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)

Full text not currently available from Enlighten.

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

University Staff: Request a correction | Enlighten Editors: Update this record

Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
384741Organocatalysts in asymmetric reactions mediated by silicon reagentsPavel KocovskyEngineering & Physical Sciences Research Council (EPSRC)GR/T27051/01CHEM - CHEMISTRY