TY - JOUR
T1 - Enantioselective carbolithiation of S-alkenyl-N-aryl thiocarbamates
T2 - Kinetic and thermodynamic control
AU - Castagnolo, Daniele
AU - Degennaro, Leonardo
AU - Luisi, Renzo
AU - Clayden, Jonathan
PY - 2015/2/28
Y1 - 2015/2/28
N2 - The addition of n-butyllithium to alkenylthiocarbamates in the presence of (-)-sparteine or the (+)-sparteine surrogate leads to asymmetric carbolithiation, and returns enantiomerically enriched thiocarbamate derivatives of secondary thiols. In THF, with the (+)-sparteine surrogate, in situ aryl migration leads to an enantiomerically enriched tertiary thiol derivative. Remarkably, the two pseudoenantiomeric chiral ligands do not always give enantiomeric products, probably as a result of a complex interplay of kinetic and thermodynamic control. In situ IR and NMR studies of a stable, hindered lithiated thiocarbamate demonstrated its chemical and configurational stability over a period of hours at 0 °C. This journal is
AB - The addition of n-butyllithium to alkenylthiocarbamates in the presence of (-)-sparteine or the (+)-sparteine surrogate leads to asymmetric carbolithiation, and returns enantiomerically enriched thiocarbamate derivatives of secondary thiols. In THF, with the (+)-sparteine surrogate, in situ aryl migration leads to an enantiomerically enriched tertiary thiol derivative. Remarkably, the two pseudoenantiomeric chiral ligands do not always give enantiomeric products, probably as a result of a complex interplay of kinetic and thermodynamic control. In situ IR and NMR studies of a stable, hindered lithiated thiocarbamate demonstrated its chemical and configurational stability over a period of hours at 0 °C. This journal is
UR - http://www.scopus.com/inward/record.url?scp=84922768397&partnerID=8YFLogxK
U2 - 10.1039/c4ob02329c
DO - 10.1039/c4ob02329c
M3 - Article (Academic Journal)
C2 - 25562487
AN - SCOPUS:84922768397
SN - 1477-0520
VL - 13
SP - 2330
EP - 2340
JO - Organic and Biomolecular Chemistry
JF - Organic and Biomolecular Chemistry
IS - 8
ER -