| Abstract: | A desymmetrization strategy was developed involving iridium‐catalyzed allylic dearomatization of indoles. The six‐membered‐ring spiroindolenines contain three contiguous stereogenic centers, including an all‐carbon quaternary center, and were obtained in up to 99 % yield with 99 % ee and >95:5 d.r. When treated with a catalytic amount of tosylic acid, six‐membered spiroindolenine undergoes an unprecedented six‐to‐seven‐membered ring expansion, affording the corresponding hexahydroazepino4,5‐b ]indole. |
