Selectivity Switch in a Rhodium(II) Carbene Triggered Cyclopentannulation: Divergent Access to Three Polycyclic Indolines

A selectivity switch in a RhII/carbene‐triggered cyclopentannulation with catalytic InCl3 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...

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Bibliographic Details
Published in:Angewandte Chemie 2019-03, Vol.131 (13), p.4389-4393
Main Authors: Liu, Hua‐Kui, Wang, Sunewang R., Song, Xiang‐Yang, Zhao, Liu‐Peng, Wang, Lijia, Tang, Yong
Format: Article
Language:English
Subjects:
Anellierungen
Carbene
Catalysis
Chemical reactions
Chemistry
Cyclopentane
Heterocyclen
Heterocyclic compounds
Indoles
Organic chemistry
Polycyclen
Rhodium
Selectivity
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Summary:A selectivity switch in a RhII/carbene‐triggered cyclopentannulation with catalytic InCl3 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. Aus eins mach drei: Die effektive Regio‐ und Diastereoselektivitätskontrolle einer Cyclopentan‐Anellierung liefert drei polycyclische Indoline aus den gleichen Ausgangsverbindungen. Der Zugang zu den jeweiligen Produkten ergibt sich aus einer einfachen Änderung von Lösungsmittel und Reaktionstemperatur.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201812294