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

Andrei V. Malkov; Sigitas Stončius; Mark Bell; Fabiomassumi Castelluzzo; Pedro Ramírez-López; Lada Biedermannová; Vratislav Langer; Lubomir Rulíšek; Pavel Kočovský

doi:10.1002/chem.201203817

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)

Research output: Contribution to journal › Article › peer-review

39 Citations (Scopus)

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 language	English
Pages (from-to)	9167-9185
Number of pages	19
Journal	Chemistry: a European Journal
Volume	19
Issue number	28
DOIs	https://doi.org/10.1002/chem.201203817
Publication status	Published - 2013

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10.1002/chem.201203817

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@article{8f96405cefe34dd4b82ec6231e94941f,

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

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.",

author = "Malkov, \{Andrei V.\} and Sigitas Ston{\v c}ius and Mark Bell and Fabiomassumi Castelluzzo and Pedro Ram{\'i}rez-L{\'o}pez and Lada Biedermannov{\'a} and Vratislav Langer and Lubomir Rul{\'i}{\v s}ek and Pavel Ko{\v c}ovsk{\'y}",

year = "2013",

doi = "10.1002/chem.201203817",

language = "English",

volume = "19",

pages = "9167--9185",

journal = "Chemistry: a European Journal",

issn = "0947-6539",

publisher = "Wiley",

number = "28",

}

Mechanistic dichotomy in the asymmetric allylation of aldehydes with allyltrichlorosilanes catalyzed by chiral pyridine N-oxides. / Malkov, Andrei V. (Lead / Corresponding author); Stončius, Sigitas (Lead / Corresponding author); Bell, Mark et al.
In: Chemistry: a European Journal, Vol. 19, No. 28, 2013, p. 9167-9185.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Mechanistic dichotomy in the asymmetric allylation of aldehydes with allyltrichlorosilanes catalyzed by chiral pyridine N-oxides

AU - Malkov, Andrei V.

AU - Stončius, Sigitas

AU - Bell, Mark

AU - Castelluzzo, Fabiomassumi

AU - Ramírez-López, Pedro

AU - Biedermannová, Lada

AU - Langer, Vratislav

AU - Rulíšek, Lubomir

AU - Kočovský, Pavel

PY - 2013

Y1 - 2013

N2 - 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.

AB - 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.

UR - https://www.scopus.com/pages/publications/84879881526

U2 - 10.1002/chem.201203817

DO - 10.1002/chem.201203817

M3 - Article

C2 - 23744629

AN - SCOPUS:84879881526

SN - 0947-6539

VL - 19

SP - 9167

EP - 9185

JO - Chemistry: a European Journal

JF - Chemistry: a European Journal

IS - 28

ER -

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

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