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Relevant academic research and scientific papers

Oxidative Cleavage of Alkenes by O2with a Non-Heme Manganese Catalyst

The oxidative cleavage of C═C double bonds with molecular oxygen to produce carbonyl compounds is an important transformation in chemical and pharmaceutical synthesis. In nature, enzymes containing the first-row transition metals, particularly heme and non-heme iron-dependent enzymes, readily activate O2 and oxidatively cleave C═C bonds with exquisite precision under ambient conditions. The reaction remains challenging for synthetic chemists, however. There are only a small number of known synthetic metal catalysts that allow for the oxidative cleavage of alkenes at an atmospheric pressure of O2, with very few known to catalyze the cleavage of nonactivated alkenes. In this work, we describe a light-driven, Mn-catalyzed protocol for the selective oxidation of alkenes to carbonyls under 1 atm of O2. For the first time, aromatic as well as various nonactivated aliphatic alkenes could be oxidized to afford ketones and aldehydes under clean, mild conditions with a first row, biorelevant metal catalyst. Moreover, the protocol shows a very good functional group tolerance. Mechanistic investigation suggests that Mn-oxo species, including an asymmetric, mixed-valent bis(μ-oxo)-Mn(III,IV) complex, are involved in the oxidation, and the solvent methanol participates in O2 activation that leads to the formation of the oxo species.

Photo-induced oxidative cleavage of C-C double bonds of olefins in water

The carbonyl compounds, synthesized by the oxidative cleavage of their corresponding olefins, are of great significance in organic synthesis, especially aryl ketones. We have developed a gentle and effective protocol, using acid red 94 as the organic metal-free photocatalyst, O2 as the oxidant, and water as the solvent. Under visible light irradiation, aryl ketone derivatives were obtained in moderate to excellent yields, showing good economic and environmental advantages.

A metal-free heterogeneous photocatalyst for the selective oxidative cleavage of CC bonds in aryl olefins: via harvesting direct solar energy

Selective cleavage of CC bonds is highly important for the synthesis of carbonyl containing fine chemicals and pharmaceuticals. Novel methodologies such as ozonolysis reactions, Lemieux-Johnson oxidation reaction etc. already exist. Parallel to these, catalytic methods using homogeneous catalysts also have been discovered. Considering the various advantages of heterogeneous catalysts such as recyclability and stability, couple of transition metal-based heterogeneous catalysts have been applied for this reaction. However, the pharmaceutical industries prefer to use metal-free catalysts (especially transition metal-free) to avoid further leaching in the final products. This is for sure a big challenge to an organic chemist and to the pharmaceutical industries. To make this feasible, a mild and efficient protocol has been developed using polymeric carbon nitrides (PCN) as metal-free heterogeneous photocatalysts to convert various olefins into the corresponding carbonyls. Later, this catalyst has been applied in the gram scale synthesis of pharmaceutical drugs using direct solar energy. Detailed mechanistic studies revealed the actual role of oxygen, the catalyst, and the light source.

Facile Synthesis of BiVO4 for Visible-Light-Induced C?C Bond Cleavage of Alkenes to Generate Carbonyls

BiVO4 crystals synthesized by an ultrasonic-assisted method (Sono-BiVO4) showed improved efficiency as a heterogeneous photocatalyst under visible-light irradiation. Sono-BiVO4 was successfully used for the C?C bond cleavage of alkenes to generate carbonyl compounds. Styrene derivatives were converted into carbonyl compounds in the presence of Sono-BiVO4 under highly sustainable conditions requiring only natural sources, that is, molecular oxygen, visible light, and water at room temperature. Additionally, Sono-BiVO4 could be easily separated from the reaction mixture and reused.

Thiyl radical promoted chemo- and regioselective oxidation of CC bonds using molecular oxygen: Via iron catalysis

The first example of the thiyl radical promoted ligand-free iron-catalyzed oxidative cleavage of alkenes using molecular oxygen (1 atm) has been developed. The reaction proceeds under mild reaction conditions with high efficiency and high chemo- and regioselectivity. It features a broad substrate scope and excellent functional group compatibility, enabling facile access to valuable molecules for application in medicinal chemistry. Preliminary mechanistic studies reveal that a vital intermediate dioxetane might be involved in the reaction and a thiyl radical plays a synergistic role in facilitating the selective oxidation of the CC bond.

A Continuous-Flow Process for Palladium-Catalyzed Olefin Cleavage by using Oxygen within the Explosive Regime

A continuous-flow protocol for Pd-catalyzed olefin cleavage by using molecular oxygen as the sole oxidant to give carbonyl compounds was explored. The developed flow protocol allowed the use of a low catalyst loading (0.1 mol %), and decomposition of the active catalyst was prevented through stabilization by poly(ethylene glycol)-400 (PEG-400), which was present as a cosolvent. Radical scavengers inhibited the reaction, which indicated the involvement of a free-radical path in the reaction mechanism. The applicability of the continuous-flow protocol was demonstrated on several olefin substrates. The continuous-flow process enabled safe and scalable olefin cleavage.

Catalytic Carbocation Generation Enabled by the Mesolytic Cleavage of Alkoxyamine Radical Cations

A new catalytic method is described to access carbocation intermediates via the mesolytic cleavage of alkoxyamine radical cations. In this process, electron transfer between an excited state oxidant and a TEMPO-derived alkoxyamine substrate gives rise to a radical cation with a remarkably weak C?O bond. Spontaneous scission results in the formation of the stable nitroxyl radical TEMPO.as well as a reactive carbocation intermediate that can be intercepted by a wide range of nucleophiles. Notably, this process occurs under neutral conditions and at comparatively mild potentials, enabling catalytic cation generation in the presence of both acid sensitive and easily oxidized nucleophilic partners.

AIBN-catalyzed oxidative cleavage of gem -disubstituted alkenes with O 2 as an oxidant

A 2,2-azobis(isobutyronitrile) (AIBN) catalyzed oxidative cleavage of gem-disubstituted alkenes with molecular oxygen as the oxidant has been described. Carbonyl compounds were obtained as the desired products in high yield under mild conditions. Based on previous documents and current experimental results, a relatively reasonable mechanism is proposed.

Facile synthesis of dihydrochalcones via the AlCl3-promoted tandem Friedel-Crafts acylation and alkylation of arenes with 2-alkenoyl chlorides

Tandem Friedel-Crafts acylation and alkylation of arenes with 2-alkenoyl chlorides were investigated under the catalysis of Lewis acids. The cascade reaction affords dihydrochalcones in good yields accompanying 1-indanone derivatives in some cases, in the presence of anhydrous aluminum chloride. The scope, limitation, and mechanism of the tandem reaction were also explored. The intermolecular Friedel-Crafts alkylation for the formation of dihydrochalcones is more favorable than the intramolecular one for the generation of 1-indanones in the tandem reaction due to a stable six-membered ring transition state. The sequent process was further studied by the DFT computations at the M06-2X/6-31G(d) level, which are in great agreement with the experimental observation and support the proposed mechanism. The current method provides a convenient and economic method to synthesis of dihydrochalcones.

Continuous flow ozonolysis in a laboratory scale reactor

Several important types of ozonolysis reactions have been performed in a continuous flow device that is able to perform both the ozonolysis and quenching steps in flow mode. This technique allows safe and scalable ozonolysis reactions to be performed on a laboratory scale.(Figure Presented)