Premium
Selectivity Switch in a Rhodium(II) Carbene Triggered Cyclopentannulation: Divergent Access to Three Polycyclic Indolines
Author(s) -
Liu HuaKui,
Wang Sunewang R.,
Song XiangYang,
Zhao LiuPeng,
Wang Lijia,
Tang Yong
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201812294
Subject(s) - indoline , chemistry , carbene , selectivity , rhodium , cyclopentane , annulation , intramolecular force , indole test , diastereomer , bicyclic molecule , catalysis , photochemistry , stereochemistry , medicinal chemistry , organic chemistry
A selectivity switch in a Rh II /carbene‐triggered cyclopentannulation with catalytic InCl 3 is reported for the first time, affording both diastereomers of the fused spiroindolines and an unusual bridged tetracyclic indoline in high yields with excellent selectivities. Mechanistic studies indicate an intramolecular annulation of the indole with an in situ formed aminocyclopropane. The stepwise thermal conversions from the kinetic spiroindoline to the metastable bridged indoline, and then to the thermodynamic spiroindoline, involving a ring‐opening rearrangement of a cyclopentane, is crucial for selectivity control.