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. 2018 May 28;57(22):6686-6690.
doi: 10.1002/anie.201803539. Epub 2018 May 2.

Electrochemical Functional-Group-Tolerant Shono-type Oxidation of Cyclic Carbamates Enabled by Aminoxyl Mediators

Fei Wang  1 , Mohammad Rafiee  1 , Shannon S Stahl  1
Affiliations

Electrochemical Functional-Group-Tolerant Shono-type Oxidation of Cyclic Carbamates Enabled by Aminoxyl Mediators

Fei Wang et al. Angew Chem Int Ed Engl. .

Abstract

An electrochemical method has been developed for α-oxygenations of cyclic carbamates by using a bicyclic aminoxyl as a mediator and water as the nucleophile. The mediated electrochemical process enables substrate oxygenation to proceed at a potential that is approximately 1 V lower than the redox potential of the carbamate substrate. This feature allows for functional-group compatibility that is inaccessible with conventional Shono oxidations, which proceed by direct electrochemical substrate oxidation. This reaction also represents the first α-functionalization of non-activated cyclic carbamates with oxoammonium oxidants.

Keywords: Shono oxidation; aminoxyls; carbamate; electrolysis; hydride transfer.

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Conflict of interest statement

Conflict of interest:

The authors declare no conflict of interest.

Figures

Figure 1.
Figure 1.
Reactions with different mediators (1H NMR yields with mesitylene as internal standard).
Figure 2.
Figure 2.
Reaction time course (a) and proposed mechanism (b).
Scheme 1.
Scheme 1.
Alpha-functionalization of cyclic carbamates.
Scheme 2.
Scheme 2.
Limitations in conventional Shono oxidation..
Scheme 3.
Scheme 3.. Comparison of different α -functionalization conditions for a series of different substrates.
[a] Yields of hydroxylated products. [b] 40 equiv of H2O @ 3 mA, 40 mol% ABNO. [c] 30 equiv of H2O @ 5 mA, 60 mol% PhCO2ABNO. [d] 50 equiv of H2O @ 5 mA, 60 mol% ketoABNO.1H NMR yield was shown with mesitylene as internal standard.
See this image and copyright information in PMC

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