Diastereocontrolled Construction of Spiroindolenines via Hexafluoroisopropanol-Promoted Dearomative Epoxide-Indole
Raju Chouhan1, Hemanga Bhattacharyya1, Sajal Kumar Das1
1Department of Chemical Sciences, Tezpur University, Napaam, Sonitpur, Assam 784028, India.
Abstract:
Herein, we report the discovery of the ipso-selective, dearomatizing spirocyclization of indole-tethered epoxides as a fundamentally new approach for constructing spiroindolenines equipped with three contiguous stereogenic centers under complete diastereocontrol (dr >99:1) and in high yields. Promoted by hexafluoroisopropanol, the protocol features a broad substrate scope, easy scale-up, and versatile transformations of the synthesized spiroindolenines.
Related Concept Videos
Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
Preparation of Epoxides
Epoxides result from alkene oxidation, which can be achieved by a) air, b) peroxy acids, c) hypochlorous acids, and d) halohydrin cyclization.
Epoxidation with Peroxy Acids
Epoxidation of alkenes via oxidation with peroxy acids involves the conversion of a carbon–carbon double bond to an epoxide using the oxidizing agent meta-chloroperoxybenzoic acid, commonly known as MCPBA. Since the O–O bond of peroxy acids is very weak, the addition of electrophilic oxygen of...
Cycloaddition Reactions: Overview
Thermal Electrocyclic Reactions: Stereochemistry
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.

![Solid-phase Synthesis of [4.4] Spirocyclic Oximes](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F58508.jpg&w=3840&q=50)
