TY - JOUR
T1 - Asymmetric Catalysis via Cyclic, Aliphatic Oxocarbenium Ions
AU - Lee, Sunggi
AU - Kaib, Philip S.J.
AU - List, Benjamin
N1 - Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/2/15
Y1 - 2017/2/15
N2 - A direct enantioselective synthesis of substituted oxygen heterocycles from lactol acetates and enolsilanes has been realized using a highly reactive and confined imidodiphosphorimidate (IDPi) catalyst. Various chiral oxygen heterocycles, including tetrahydrofurans, tetrahydropyrans, oxepanes, chromans, and dihydrobenzofurans, were obtained in excellent enantioselectivities by reacting the corresponding lactol acetates with diverse enol silanes. Mechanistic studies suggest the reaction to proceed via a nonstabilized, aliphatic, cyclic oxocarbenium ion intermediate paired with the confined chiral counteranion.
AB - A direct enantioselective synthesis of substituted oxygen heterocycles from lactol acetates and enolsilanes has been realized using a highly reactive and confined imidodiphosphorimidate (IDPi) catalyst. Various chiral oxygen heterocycles, including tetrahydrofurans, tetrahydropyrans, oxepanes, chromans, and dihydrobenzofurans, were obtained in excellent enantioselectivities by reacting the corresponding lactol acetates with diverse enol silanes. Mechanistic studies suggest the reaction to proceed via a nonstabilized, aliphatic, cyclic oxocarbenium ion intermediate paired with the confined chiral counteranion.
UR - http://www.scopus.com/inward/record.url?scp=85013074396&partnerID=8YFLogxK
U2 - 10.1021/jacs.6b11993
DO - 10.1021/jacs.6b11993
M3 - Article
C2 - 28169541
AN - SCOPUS:85013074396
SN - 0002-7863
VL - 139
SP - 2156
EP - 2159
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 6
ER -