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 - http://www.scopus.com/inward/record.url?scp=84879881526&partnerID=8YFLogxK
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 -