Selective Oxidative Cleavage of Alkenes

The oxidative cleavage of carbon–carbon double bonds in alkenes into discrete carbonyl compounds represents a fundamental transformation in organic synthesis. This process enables the conversion of simple olefins into ketones, aldehydes and carboxylic acids, facilitating the construction of complex molecules from readily available feedstocks. Classical methods, such as ozonolysis or permanganate oxidation, provide broad applicability but often suffer from over-oxidation, harsh conditions and poor functional-group tolerance. In response, recent advances have focused on catalytic and sustainable approaches that deliver high chemoselectivity under mild conditions. Innovations include transition-metal catalysis, photoredox strategies and electrochemical mediation, each exploiting distinct mechanistic pathways to activate molecular oxygen or benign oxidants. These modern protocols offer enhanced selectivity for nonactivated and functionalised alkenes, operational simplicity and compatibility with diverse functional groups. Applications span late-stage modification of pharmaceuticals, biomass valorisation and the sustainable upgrade of petrochemical derivatives, underlining the global significance of selective alkene cleavage in fine-chemical manufacture and materials science.

Research from Nature Portfolio

Recent studies have introduced an electrochemical approach in which nitrate salts function both as anodic mediator and supporting electrolyte to achieve oxo-functionalisation of cyclic alkanes and alkenes. This metal-free protocol employs molecular oxygen as the cathodic oxidant, enabling the efficient conversion of cyclic olefins into ketones and diacids with high atom economy and recyclability of the mediator. By coupling anodic oxidation with oxygen reduction, this method avoids stoichiometric oxidants and transition metals, offering a sustainable route for transforming petrochemical feedstocks into synthetically valuable fine chemicals.

A complementary study has developed a water-mediated, redox-neutral photoredox strategy for the deconstruction of arylalkenes. Visible-light irradiation triggers anti-Markovnikov hydration to form an alcohol intermediate, followed by photoredox cleavage of the carbon–carbon bond. Ethyl thioglycolate serves as an optimal hydrogen-atom shuttle, ensuring high chemoselectivity among competing pathways. The process yields arenes and carbonyl fragments under ambient conditions, exemplifying a redox-neutral alternative to classical oxidative deconstruction with potential for late-stage molecular editing.

Selective Oxidative Cleavage of Alkenes publication trend

The graph below shows the total number of articles in selective oxidative cleavage of alkenes across all publications each year (not limited to Nature Index journals).

Technical terms

Oxidative cleavage: Selective breaking of a carbon–carbon double bond to form carbonyl compounds.

Photoredox catalysis: Use of light and a photocatalyst to drive redox reactions via radical intermediates.

Electrochemical mediator: A redox-active species that facilitates selective electron transfer at an electrode surface.

Hydrogen-atom transfer (HAT): Radical-mediated abstraction or donation of a hydrogen atom between species.

Non-heme manganese catalyst: A manganese complex that mimics enzymatic oxidation without a heme cofactor.

References

1. Electrochemical oxo-functionalization of cyclic alkanes and alkenes using nitrate and oxygen. Nature Communications (2023).
2. Oxidative Cleavage of Alkenes by O2 with a Non-Heme Manganese Catalyst. Journal of the American Chemical Society (2021).
3. Cu-catalyzed oxygenation of alkene-tethered amides with O 2 via unactivated C[double bond, length as m-dash]C bond cleavage: a direct approach to cyclic imides. Chemical Science (2019).
4. One‐pot multistep electrochemical strategy for the modular synthesis of epoxides, glycols, and aldehydes from alkenes. Electrochemical Science Advances (2021).
5. Water mediated redox-neutral cleavage of arylalkenes via photoredox catalysis. Nature Communications (2024).