Blue LED-Promoted Syntheses of Phosphorothioates and Phosphorodithioates
Bo-Ru Shen, Pratheepkumar Annamalai, Shih-Fang Wang, Rekha Bai and Chin-Fa Lee*
*Department of Chemistry, National Chung Hsing University, Taichung City, Taiwan 402, R.O.C.,
Email: cfaleedragon.nchu.edu.tw
B.-R. Shen, P. Annamalai, S.-F. Wang, R. Bai, C.-F. Lee, J. Org. Chem., 2022, 87, 8858-8870.
DOI: 10.1021/acs.joc.2c00323
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Abstract
Blue LED irradition promotes an environmentally friendly synthesis of phosphorochalcogenoates, phosphorochalcogenothioates, and phosphinothioates in very good yields under under metal-free, ligand-free, oxidant-free, and photocatalyst-free conditions with minimum chemical waste generation and high atom economy.
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Details
The article discusses an environmentally friendly method for synthesizing phosphorothioates, phosphorodithioates, and related compounds using blue LED light. This method avoids the use of metals, ligands, oxidants, and photocatalysts, resulting in minimal chemical waste and high atom economy. The blue LED-promoted P−S, P−Se, and P−Te bond formations were optimized using various bases and solvents, with ethyl acetate and NEt3 proving most effective. The method achieved good to excellent yields for a wide range of substrates, including aryl disulfides, diselenides, and ditellurides. The protocol was also effective for large-scale synthesis and demonstrated high synthetic utility by producing agrochemicals like inezin and iprobenfos. Control experiments suggested a radical pathway for the bond formation. The study highlights the potential of visible-light-mediated reactions in green chemistry, offering a sustainable approach to synthesizing valuable phosphorus-containing compounds. The research was supported by various Taiwanese institutions and the Ministry of Science and Technology, Taiwan.
Key Words
Phosphorothioates, Phosphorodithioates
ID: J42-Y2022