Palladium-catalyzed α-arylation of nitroalkanes with aryl triflates through the C(sp2)−C(sp3) bond coupling

• Published in: Journal of molecular structure 2023-08, Vol.1286, p.135565, Article 135565
• Main Authors: Hu, Sengui, He, Xiaoyu, Lei, Zhiguo, Yu, Lin, Duan, Wengui
• Format: Article
• Language: English
• Subjects: Aryl triflates; Palladium; Sustainable route; α-Arylated nitroalkanes
• ISSN: 0022-2860; 1872-8014
• DOI: 10.1016/j.molstruc.2023.135565

•An efficient method for the synthesis of high-valued α-arylated nitroalkanes.•Using phenol derivatives acting as sustainable arylating reagents.•Pd/BrettPhos complex exhibits high catalytic activity in the activation of C − O bond.•Construction of C(sp2)−C(sp3) bond via cleavage of C − O bond under mild condition. Herein, we present an efficient and practical method for the synthesis of α-arylated nitroalkanes through palladium-catalyzed cross-coupling of nitroalkanes and phenol derivatives under mild conditions. The key to this success lies in using BrettPhos as a ligand. Compared with the known methods, this method is more novel and environmentally friendly by using phenol derivatives acting as arylating reagents, which can be obtained from naturally abundant lignins. The substrates bearing electron-donating or electron-withdrawing are compatible with the reaction, affording the α-arylated nitroalkanes in yields ranging from 50% to 90%. Furthermore, various functional groups can be tolerated, such as halide, amine, acetyl, alkene, ester, ether, and thioether. Through the use of the newly developed protocol, simple starting materials can be converted to α-arylated nitroalkanes, which are versatile synthetic intermediates for the preparation of aryl ketones, oximes, nitriles, chiral amines, etc.