Selective Oxyfunctionalization of Benzylic C–H with No Solvent

• Published in: Journal of organic chemistry Vol. 89; no. 22; pp. 16645 - 16652
• Main Authors: Tian, Miao, Li, Jinya, Mou, Quansheng, Liu, Mingxin
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 15.11.2024; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Organic; lignin; mechanochemistry; organic chemistry; oxidation; Physical Sciences; Science & Technology; solvents; spectroscopy; CATALYZED ASYMMETRIC HYDROGENATION; FUNCTIONALIZATION; OXYGEN; ORGANIC-MOLECULES; ACID; BONDS; AEROBIC OXIDATION; COPPER; HYDROXYPHTHALIMIDE; BENZALDEHYDES
• ISSN: 0022-3263; 1520-6904; 1520-6904
• DOI: 10.1021/acs.joc.4c01950

The direct selective oxyfunctionalization of C–H into CO represents a highly useful, yet challenging, synthetic methodology. Herein, a one-step oxyfunctionalization of benzylic C–H into aryl ketone, with no overoxidation of the −OH functional group, is reported through mechanochemistry. The substrate scope is also tolerant of a wide range of different functional groups, providing a particularly sustainable yet widely adaptable route for the synthesis of aryl ketones, which represent both a classic synthetic precursor and a useful strategy for lignin monomer valorization. A series of mechanistic and spectroscopic investigations were also conducted to shed light on the unique C–H over −OH selectivity, opening up new avenues for oxidation chemistry.