Copper-Catalyzed α-Arylation of Nitroalkanes with (Hetero)aryl Bromides/Iodides

Huang，Jianqiang1; Li，Taian1; Lu，Xiaobiao1; Ma，Dawei1,2

2024-02-12

10.1002/anie.202315994

Angewandte Chemie - International Edition   影响因子和分区

1433-7851

1521-3773

α-Aryl substituted nitroalkanes are valuable synthetic building blocks that can be easily converted into α-aryl substituted aldehydes, ketones, carboxylic acids, as well as amines. Herein, an efficient Cu/oxalamide-catalyzed coupling between nitroalkanes and (hetero)aryl halides (Br, I) was developed to direct access highly diverse α-aryl substituted nitroalkanes. Compared with the current state of art, this protocol is more environmentally friendly and practical for synthetic chemists. This approach is characterized by a broad substrate scope on both nitroalkane part (primary nitroalkanes and nitromethane) and sp halide part ((hetero)aryl bromides/iodides and alkenyl bromides/iodides). The excellent functional group tolerance was observed, which would enable real world synthetic applications. More importantly, TON of current transformation reached to 3640, when some aryl iodides were used as coupling partners. This represents currently the highest catalyst turnover for transition-metal catalyzed α-arylation of nitroalkanes. Furthermore, the successful application in late-stage modification of complex molecules and synthesis of a known retinoid X receptor (RXR) antagonist exemplified its synthetic potential.

(Hetero)Aryl Halides Copper Cross-Coupling Ligands α-Aryl Nitroalkanes

SCI ; EI

英语

第一 ; 通讯

CHEMISTRY

2-s2.0-85181911399

Scopus

1.Shenzhen Key Laboratory of Cross-Coupling Reactions,Southern University of Science and Technology (SUSTech),Department of Chemistry,Southern University of Science and Technology (SUSTech),Shenzhen,518055,China
2.State Key Laboratory of Chemical Biology,Shanghai Institute of Organic Chemistry,University of Chinese Academy of Sciences,Chinese Academy of Sciences,Shanghai,345 Lingling Lu,200032,China

Huang，Jianqiang,Li，Taian,Lu，Xiaobiao,et al. Copper-Catalyzed α-Arylation of Nitroalkanes with (Hetero)aryl Bromides/Iodides[J]. Angewandte Chemie - International Edition,2024,63(7).

Huang，Jianqiang,Li，Taian,Lu，Xiaobiao,&Ma，Dawei.(2024).Copper-Catalyzed α-Arylation of Nitroalkanes with (Hetero)aryl Bromides/Iodides.Angewandte Chemie - International Edition,63(7).

Huang，Jianqiang,et al."Copper-Catalyzed α-Arylation of Nitroalkanes with (Hetero)aryl Bromides/Iodides".Angewandte Chemie - International Edition 63.7(2024).