TY - JOUR
T1 - Stereoselective Dynamic Cyclization of Allylic Azides
T2 - Synthesis of Tetralins, Chromanes, and Tetrahydroquinolines
AU - Porter, Matthew R.
AU - Shaker, Rami M.
AU - Calcanas, Cristian
AU - Topczewski, Joseph J.
N1 - Publisher Copyright:
© 2018 American Chemical Society.
PY - 2018/1/31
Y1 - 2018/1/31
N2 - This report describes the stereoselective synthesis of 3-azido-tetralins, -chromanes, and -tetrahydroquinolines via a tandem allylic azide rearrangement/Friedel-Crafts alkylation. Exposure of allylic azides with a pendant trichloroacetimidate to catalytic quantities of AgSbF6 proved optimal for this transformation. This cascade successfully differentiates the equilibrating azide isomers, providing products in excellent yield and selectivity (>25 examples, up to 94% yield and >25:1 dr). In many cases, the reactive isomer is only a trace fraction of the equilibrium mixture, keenly illustrating the dynamic nature of these systems. We demonstrate the utility of this process via a synthesis of hasubanan.
AB - This report describes the stereoselective synthesis of 3-azido-tetralins, -chromanes, and -tetrahydroquinolines via a tandem allylic azide rearrangement/Friedel-Crafts alkylation. Exposure of allylic azides with a pendant trichloroacetimidate to catalytic quantities of AgSbF6 proved optimal for this transformation. This cascade successfully differentiates the equilibrating azide isomers, providing products in excellent yield and selectivity (>25 examples, up to 94% yield and >25:1 dr). In many cases, the reactive isomer is only a trace fraction of the equilibrium mixture, keenly illustrating the dynamic nature of these systems. We demonstrate the utility of this process via a synthesis of hasubanan.
UR - http://www.scopus.com/inward/record.url?scp=85041369197&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85041369197&partnerID=8YFLogxK
U2 - 10.1021/jacs.7b11299
DO - 10.1021/jacs.7b11299
M3 - Article
C2 - 29303567
AN - SCOPUS:85041369197
SN - 0002-7863
VL - 140
SP - 1211
EP - 1214
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 4
ER -