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

Andrei V. Malkov (Lead / Corresponding author), Sigitas Stončius (Lead / Corresponding author), Mark Bell, Fabiomassumi Castelluzzo, Pedro Ramírez-López, Lada Biedermannová, Vratislav Langer, Lubomir Rulíšek (Lead / Corresponding author), Pavel Kočovský (Lead / Corresponding author)

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    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.
    Original languageEnglish
    Pages (from-to)9167-9185
    Number of pages19
    JournalChemistry: a European Journal
    Volume19
    Issue number28
    DOIs
    Publication statusPublished - 2013

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    Malkov, A. V., Stončius, S., Bell, M., Castelluzzo, F., Ramírez-López, P., Biedermannová, L., Langer, V., Rulíšek, L., & 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), 9167-9185. https://doi.org/10.1002/chem.201203817