Metal‐Free Electrocatalytic Diacetoxylation of Alkenes

1,2‐Dioxygenation of alkenes leads to a structural motif ubiquitous in organic synthons, natural products and active pharmaceutical ingredients. Straightforward and green synthesis protocols starting from abundant raw materials are required for facile and sustainable access to these crucial moieties...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2023-12, Vol.62 (49), p.e202311539-n/a
Main Authors: Vanhoof, Jef R., De Smedt, Pieter J., Derhaeg, Jan, Ameloot, Rob, De Vos, Dirk E.
Format: Article
Language:English
Subjects:
Acetic acid
Alkenes
Anodizing
Catalysts
Electrochemistry
Functional groups
Hypervalent Compounds
Natural products
Oxidation
Propylene
Raw materials
Reaction Mechanisms
Substrates
Synthetic Methods
Transition metals
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Summary:1,2‐Dioxygenation of alkenes leads to a structural motif ubiquitous in organic synthons, natural products and active pharmaceutical ingredients. Straightforward and green synthesis protocols starting from abundant raw materials are required for facile and sustainable access to these crucial moieties. Especially industrially abundant aliphatic alkenes have proven to be arduous substrates in sustainable 1,2‐dioxygenation methods. Here, we report a highly efficient electrocatalytic diacetoxylation of alkenes under ambient conditions using a simple iodobenzene mediator and acetic acid as both the solvent and an atom‐efficient reactant. This transition metal‐free method is applicable to a wide range of alkenes, even challenging feedstock alkenes such as ethylene and propylene, with a broad functional group tolerance and excellent faradaic efficiencies up to 87 %. In addition, this protocol can be extrapolated to alkenoic acids, resulting in cyclization of the starting materials to valuable lactone derivatives. With aromatic alkenes, a competing mechanism of direct anodic oxidation exists which enables reaction under catalyst‐free conditions. The synthetic method is extensively investigated with cyclic voltammetry. A highly efficient electrocatalytic 1,2‐dioxygenation of alkenes utilizing readily available materials in ambient conditions is developed. The protocol is widely applicable to aliphatic and aromatic alkenes with excellent faradaic efficiencies and yields of up to 96 %. The versatility of the method is expanded with alkenoic acids towards lactone derivatives and with other carboxylic acids like HCOOH.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202311539