Chemo- and Diastereoselectivities in the Electrochemical Reduction of Maleimides

The electrochemical cathodic reduction of cyclic imides (maleimides) to succinimides can be achieved chemoselectively in the presence of alkene, alkyne, and benzyl groups. The efficiency of the system was demonstrated by using a 3D electrode in a continuous flow reactor. The reduction of 3,4‐dimethy...

Full description

Saved in:
Bibliographic Details
Published in:ChemSusChem 2015-02, Vol.8 (4), p.665-671
Main Authors: Rix, Kathryn, Kelsall, Geoffrey H., Hellgardt, Klaus, Hii, King Kuok (Mimi)
Format: Article
Language:English
Subjects:
chemoselectivity
diastereoselectivity
Electrochemistry
Electrodes
Maleimides - chemistry
Oxidation-Reduction
reaction mechanisms
reduction
Stereoisomerism
Succinimides - chemistry
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:The electrochemical cathodic reduction of cyclic imides (maleimides) to succinimides can be achieved chemoselectively in the presence of alkene, alkyne, and benzyl groups. The efficiency of the system was demonstrated by using a 3D electrode in a continuous flow reactor. The reduction of 3,4‐dimethylmaleimides to the corresponding succinimides proceeds with a 3:2 diastereomeric ratio, which is independent of the nitrogen substituent and electrode surface area. The stereoselectivity of the process was rationalized by using DFT calculations, involving an acid‐catalyzed tautomerization of a half‐enol occurring through a double hydrogen‐transfer mechanism. Reduce with precision: The efficiency and selectivity of the electrochemical reduction of maleimide derivatives are examined in a continuous‐flow reactor. The stereoselectivity of the process can be rationalized by using DFT calculations.
ISSN:1864-5631
1864-564X
DOI:10.1002/cssc.201403184