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Phosphonate-Substituted Pyrazinoporphyrin - a General Photocatalyst for Efficient Sulfoxidation
Daria A Polivanovskaia1, Inna A Abdulaeva1, Kirill P Birin1
1Frumkin Institute of Physical Chemistry and Electrochemistry RAS, Leninsky pr., 31, bldg. 4, Moscow, 119071, Russia.
Chempluschem
|September 11, 2024
Summary
Pyrazine-annelated porphyrin acts as a highly efficient photocatalyst for aerobic sulfide oxidation. This photosensitizer enables high conversion and selectivity for various sulfides, even on a gram scale.
Area of Science:
- Organic Chemistry
- Photocatalysis
- Green Chemistry
Background:
- Organic sulfides are versatile chemical intermediates.
- Efficient and selective oxidation of sulfides to sulfoxides is crucial in organic synthesis.
- Developing robust and reusable photocatalysts is a key goal in sustainable chemistry.
Purpose of the Study:
- To demonstrate the exceptional efficiency of pyrazine-annelated porphyrin as a general photocatalyst for sulfide oxidation.
- To investigate the influence of reaction conditions on photocatalytic sulfoxidation.
- To achieve high conversion and selectivity in aerobic photooxidation of diverse sulfides.
Main Methods:
- Synthesis and characterization of phosphonate-substituted pyrazinoporphyrin 2H-1.
- Aerobic photooxidation of various organic sulfides using the synthesized photosensitizer.
- Optimization of reaction conditions, focusing on solvent systems and methanol ratios.
- Analysis of reaction efficiency, conversion, selectivity, turnover number, and turnover frequency.
Main Results:
- Pyrazinoporphyrin 2H-1 exhibited excellent photostability and high efficiency in aerobic sulfide photooxidation.
- Methanol as a solvent component was critical for high photocatalytic sulfoxidation efficiency.
- Complete conversion (97-100%) and high selectivity (96-100%) were achieved for a wide range of sulfides at low catalyst loading (0.001 mol%).
- Exceptional turnover numbers (up to 100,000) and turnover frequencies (up to 6250 h⁻¹) were recorded.
- Gram-scale synthesis of sulfoxides yielded products in 66-96% yield and >98% purity.
Conclusions:
- Phosphonate-substituted pyrazinoporphyrin 2H-1 is a highly effective and general photocatalyst for aerobic sulfide oxidation.
- The developed method offers a sustainable and efficient route for sulfoxide synthesis.
- The catalyst's performance, including high turnover numbers and gram-scale applicability, highlights its potential for industrial applications.
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