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. 2019 Nov 15;21(22):9241-9246.
doi: 10.1021/acs.orglett.9b03652. Epub 2019 Nov 5.

Manganese-Catalyzed Electrochemical Deconstructive Chlorination of Cycloalkanols via Alkoxy Radicals

Benjamin D W Allen  1 , Mishra Deepak Hareram  1 , Alex C Seastram  1 , Tom McBride  1 , Thomas Wirth  2 , Duncan L Browne  1 , Louis C Morrill  1
Affiliations

Manganese-Catalyzed Electrochemical Deconstructive Chlorination of Cycloalkanols via Alkoxy Radicals

Benjamin D W Allen et al. Org Lett. .

Erratum in

Abstract

A manganese-catalyzed electrochemical deconstructive chlorination of cycloalkanols has been developed. This electrochemical method provides access to alkoxy radicals from alcohols and exhibits a broad substrate scope, with various cyclopropanols and cyclobutanols converted into synthetically useful β- and γ-chlorinated ketones (40 examples). Furthermore, the combination of recirculating flow electrochemistry and continuous inline purification was employed to access products on a gram scale.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Context and Outline of Electrochemical Strategy
Scheme 2
Scheme 2. Substrate Scope: Batch and Flow Electrochemistry
Reactions performed with 0.3 mmol of cycloalkanol using the ElectraSyn 2.0 batch electrochemical reactor with isolated yields after chromatographic purification quoted unless stated otherwise. Cycloalkanol was added over 2 h via syringe pump, TBAOAc (0.1 M) as electrolyte. TBAOAc (0.1 M) as electrolyte. Yield as determined by 1H NMR analysis of the crude reaction mixture with 1,3,5-trimethylbenzene as the internal standard. 6 h.
Scheme 3
Scheme 3. Mechanistic Studies
Yield as determined by 1H NMR analysis of the crude reaction mixture with 1,3,5-trimethylbenzene as the internal standard.
See this image and copyright information in PMC

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