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

  • Sayantan Maity‎ et al.
  • ACS omega‎
  • 2020‎

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.


Fluoresceinated Aminohexanol Tethered Inositol Hexakisphosphate: Studies on Arabidopsis thaliana and Drosophila melanogaster and Docking with 2P1M Receptor.

  • Sujeet Kumar Thakur‎ et al.
  • ACS omega‎
  • 2020‎

Inositol hexakisphosphate (InsP6; phytic acid) is considered as the second messenger and plays a very important role in plants, animals, and human beings. It is the principal storage form of phosphorus in many plant tissues, especially in dry fruits, bran, and seeds. The resulting anion is a colorless species that plays a critical role in nutrition and is believed to cure many diseases. A fluoresceinated aminohexanol tethered inositol hexakisphosphate (III) had been synthesized earlier involving many complicated steps. We describe here a simple two-step synthesis of (III) and its characterization using different techniques such as matrix-assisted laser desorption ionization mass spectrometry, tandem mass spectrometry, and Fourier transform infrared, ultraviolet-visible, ultraviolet-fluorescence, 1H nuclear magnetic resonance (NMR), and two-dimensional NMR spectroscopies. The effect of (III) has been investigated in the model systems, Arabidopsis thaliana and Drosophila melanogaster. Using Schrodinger software, computational studies on the binding of (III) with the protein 2P1M (Auxin-receptor TIR1-adaptor ASK1 complex) has revealed strong binding propensity with this compound. These studies on the fluoresceinated tethered phytic acid could have far reaching implications on its efficacy for human health and treatment of diseases (cancer/tumor and glioblastoma) and for understanding phosphorous recycling in the environment, especially for plant systems.


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