Copper-Catalyzed Asymmetric Three-Component Radical 1,2-Carboamination of Acrylamides with Arylamines: Access to Chiral α-Tertiary N-Arylamines

Fang, Jia-Heng1,2; Chen, Ji-Jun2; Du, Xuan-Yi2; Dong, Zhe2; Tian, Run-Yan2,3; Yang, Chang-Jiang3; Wang, Fu-Li2; Luan, Cheng2; Li, Zhong-Liang4; Liu, Xin-Yuan2

2024-07-01

10.31635/ccschem.024.202404389

CCS CHEMISTRY   影响因子和分区

2096-5745

The asymmetric radical carboamination of 1,1-disubstituted alkenes from readily available alkyl halides and arylamines provides expedient access to valueadded chiral alpha-tertiary N-arylamines but has been less recognized. A challenge arises mainly from the difficult reaction initiation inherent in alkyl halides and the construction of fully substituted chiral C-N bonds from sterically congested tertiary alkyl radicals. Herein, we report a copper-catalyzed asymmetric three-component radical carboamination of acrylamides utilizing an anionic chiral N,N,N-ligand under mild conditions. This ligand was essential for the reaction initiation by enhancing the reducing capability of copper and enabling the enantiocontrol over tertiary alkyl radicals. The substrate scope was broad, covering an array of acrylamides, aryl- and heteroaryl-amines, as well as alkyl halides and sulfonyl chlorides, enabling good functional group tolerance. When combined with the follow-up transformation, this strategy provides a versatile platform for accessing structurally diverse chiral alpha-tertiary N-arylamine building blocks of interest in organic synthesis.

asymmetric catalysis copper alkenes radical reactions chiral amines

ESCI

英语

通讯

National Natural Science Foundation of China (NSFC)["22025103","22331006","92256301","22371112","22101122"] ; National Key R&D Program of China["2021YFF0701604","2021YFF0701704"] ; Guangdong Major Project of Basic and Applied Basic Research, China[2023B0303000020] ; Guangdong Basic and Applied Basic Research Foundation, China[2023A1515140088] ; Shenzhen Science and Technology Program, China["JCYJ20220818100600001","JCYJ202205300115409020","20220814231741002"] ; Shenzhen Key Laboratory of Cross-Coupling Reactions, China[ZDSYS20220328104200001] ; Dongguan Key Laboratory of Interdisciplinary Science for Advanced Materials and Large-Scale Scientific Facilities, China[2023KSYS014]

Chemistry

Chemistry, Multidisciplinary

WOS:001279313800001

CHINESE CHEMICAL SOC

Web of Science

1.Harbin Inst Technol, Sch Chem & Chem Engn, Harbin 150001, Peoples R China
2.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Guangming Adv Res Inst, Dept Chem,Shenzhen Key Lab Cross Coupling Reaction, Shenzhen 518055, Peoples R China
3.Great Bay Univ, Dongguan Key Lab Data Sci & Intelligent Med, Dept Chem, Dongguan 523000, Peoples R China
4.Great Bay Univ, Sch Phys Sci, Dongguan Key Lab Interdisciplinary Sci Adv Mat & L, Dongguan 523000, Peoples R China

Fang, Jia-Heng,Chen, Ji-Jun,Du, Xuan-Yi,et al. Copper-Catalyzed Asymmetric Three-Component Radical 1,2-Carboamination of Acrylamides with Arylamines: Access to Chiral α-Tertiary N-Arylamines[J]. CCS CHEMISTRY,2024.

Fang, Jia-Heng.,Chen, Ji-Jun.,Du, Xuan-Yi.,Dong, Zhe.,Tian, Run-Yan.,...&Liu, Xin-Yuan.(2024).Copper-Catalyzed Asymmetric Three-Component Radical 1,2-Carboamination of Acrylamides with Arylamines: Access to Chiral α-Tertiary N-Arylamines.CCS CHEMISTRY.

Fang, Jia-Heng,et al."Copper-Catalyzed Asymmetric Three-Component Radical 1,2-Carboamination of Acrylamides with Arylamines: Access to Chiral α-Tertiary N-Arylamines".CCS CHEMISTRY (2024).