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Phosphorous-Doped Graphitic Material as a Solid Acid Catalyst for Microwave-Assisted Synthesis of β-Ketoenamines and Baeyer–Villiger Oxidation

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Synthesis of phosphorous-doped graphitic materials (P-Gc) using phytic acid as a precursor was done in a microwave oven in a cost- and time-effective green way. The material was used as… Click to show full abstract

Synthesis of phosphorous-doped graphitic materials (P-Gc) using phytic acid as a precursor was done in a microwave oven in a cost- and time-effective green way. The material was used as a solid acid catalyst for microwave (MW)-assisted synthesis of β-ketoenamines and Baeyer–Villiger (BV) oxidation. In the case of BV oxidation, hydrogen peroxide (H2O2) was used as a green oxidant. For β-ketoenamines, in most cases, 100% conversion with an ∼95% yield was achieved in ethyl acetate medium. In solvent-free conditions, the yield of β-ketoenamines was ∼75%. A kinetic study suggested that the resonance stabilization of the positive reaction center happens in the transition state for β-ketoenamine synthesis. In BV oxidation, cyclic ketones were converted to their corresponding cyclic esters in good to high yields (∼80% yield) in a shorter reaction time (6–20 min). As per our knowledge, this is the first report of BV oxidation catalyzed by a heteroatom-doped graphitic material. For BV oxidation, the phosphoric acid functional groups present in P-Gc might increase the electrophilicity of the carbonyl group of the ketones to compensate for the weakness of H2O2 as a nucleophile and a spiro-bisperoxide intermediate has been identified in high-resolution mass spectrometry.

Keywords: solid acid; oxidation; doped graphitic; material; phosphorous doped; synthesis

Journal Title: ACS Omega
Year Published: 2020

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