Cathodic radical cyclisation of aryl halides using a strongly-reducing catalytic mediator in flow
File(s)
Author(s)
Type
Journal Article
Abstract
Electro-reductive radical cyclisation of aryl halides affords the corresponding hetero- and carbo-cycles in an undivided flow reactor equipped with steel and carbon electrodes using an organic mediator. A dissolving metal anode is not needed, and the mediator can be employed in a sub-stoichiometric amount (0.05 equiv), increasing the practical utility of cathodic radical cyclisation. The methodology is applied to O-, N-, and C-tethers, yielding tricyclic fused and spiro systems. In the absence of mediator, the major pathway is hydrogenolysis of the C−X bond, a 2 e− process occurring at the cathode. Predominance of the radical pathway in presence of a strongly reducing mediator (M) is consistent with homogeneous electron-transfer in a reaction layer detached from the cathode surface, where the flux of M.− leaving the electrode is such that little aryl halide reaches the cathode.
Date Issued
2022-08-26
Date Acceptance
2022-07-01
Citation
Angewandte Chemie International Edition, 2022, 61 (35)
ISSN
1433-7851
Publisher
Wiley
Journal / Book Title
Angewandte Chemie International Edition
Volume
61
Issue
35
Copyright Statement
© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH
This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
License URL
Identifier
http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000826548500001&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=1ba7043ffcc86c417c072aa74d649202
Subjects
Science & Technology
Physical Sciences
Chemistry, Multidisciplinary
Electrosynthesis
Flow Chemistry
Mediator
Chemistry
Radical Cyclization
Reductive Cyclization
STATE LIMITING CURRENTS
ELECTROCHEMICAL REDUCTION
ELECTROLYSIS CELL
EC PROCESSES
MICROELECTRODE
KINETICS
LIGHT
ELECTROSYNTHESIS
COMPLEXES
MECHANISM
Publication Status
Published
Article Number
ARTN e202203694
Date Publish Online
2022-07-05