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Title: Mechanistic dichotomy in the asymmetric allylation of aldehydes with allyltrichlorosilanes catalyzed by chiral pyridine N-oxides
Authors: Malkov, Andrei V.
Stoncius, Sigitas
Bell, Mark
Castelluzzo, Fabiomassimo
Ramirez-Lopez, Pedro
Biedermannova, Lada
Langer, Vratislav
Rulisek, Lubomir
Kocovsky, Pavel
Keywords: Allylation
Allylsilanes
Calculations
Organocatalysis
Pyridine N-oxides
Issue Date: 2013
Publisher: © Wiley-VCH
Citation: MALKOV, A.V. ... et al., 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.
Abstract: Detailed kinetic and computational investigation of the enantio- and diastereoselective allylation of aldehydes with allyltrichlorosilanes, employing the pyridine N-oxides METHOX and QUINOX as chiral organocatalysts, indicate that the reaction can proceed via 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 the 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.
Description: This is the peer reviewed version of the following article: MALKOV, A.V. ... et al., 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, which has been published in final form at: http://dx.doi.org/10.1002/chem.201203817.
Sponsor: We thank the EPSRC for grant No. GR/T27051/01, the Ministry of Education and Science of Spain for a fellowship to P. R.-L., the University of Glasgow for a studentship to M. B., the University of Rome for a fellowship to F. C., the Ministry of Education of the Czech Republic (MŠMT ČR) for grant No. LC512, the European Socrates-Erasmus exchange program for a scholarship to L. B., the European Social Fund under the Global Grant measure (VP1-3.1-ŠMM- 07-K-01-030), and Dr. Alfred Bader for additional support.
Version: Accepted for publication
DOI: 10.1002/chem.201203817
URI: https://dspace.lboro.ac.uk/2134/15477
Publisher Link: http://dx.doi.org/10.1002/chem.201203817
ISSN: 0947-6539
Appears in Collections:Closed Access (Chemistry)

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