Rhodium-Catalyzed Asymmetric Hydrogenation and Transfer Hydrogenation of 1,3-Dipolar Nitrones

Xu, Liren1,2; Yang, Tilong1,2; Sun, Hao1,2; Zeng, Jingwen1,2; Mu, Shuo1,2; Zhang, Xumu1,2; Chen, Gen-Qiang2,3

2024-04-02

10.1002/anie.202319662

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   影响因子和分区

1433-7851

1521-3773

Owing to their distinctive 1,3-dipolar structure, the catalytic asymmetric hydrogenation of nitrones to hydroxylamines has been a formidable and longstanding challenge, characterized by intricate enantiocontrol and susceptibility to N-O bond cleavage. In this study, the asymmetric hydrogenation and transfer hydrogenation of nitrones were accomplished with a tethered TsDPEN-derived cyclopentadienyl rhodium(III) catalyst (TsDPEN: p-toluenesulfonyl-1,2-diphenylethylene-1,2-diamine), the reaction proceeds via a novel 7-membered cyclic transition state, producing chiral hydroxylamines with up to 99 % yield and >99 % ee. The practical viability of this methodology was underscored by gram-scale catalytic reactions and subsequent transformations. Furthermore, mechanistic investigations and DFT calculations were also conducted to elucidate the origin of enantioselectivity.

1,3-dipolar nitrones asymmetric (transfer) hydrogenation hydrogen-bonding interaction 7-membered cyclic transition state

SCI ; EI

英语

第一 ; 通讯

Shenzhen Science and Technology Innovation Committee[JCYJ20210324104202007] ; Guangdong Basic and Applied Basic Research Foundation[2022B1515020055] ; National Natural Science Foundation of China["21991113","21901107","22171129"] ; null[2021YFF0701604]

Chemistry

Chemistry, Multidisciplinary

WOS:001178004600001

WILEY-V C H VERLAG GMBH

CHEMISTRY

Web of Science

1.Southern Univ Sci & Technol, Grubbs Inst, Dept Chem, Shenzhen, Peoples R China
2.Southern Univ Sci & Technol, Med X Pingshan, Shenzhen, Peoples R China
3.Southern Univ Sci & Technol, Acad Adv Interdisciplinary Studies, Shenzhen, Peoples R China

Xu, Liren,Yang, Tilong,Sun, Hao,et al. Rhodium-Catalyzed Asymmetric Hydrogenation and Transfer Hydrogenation of 1,3-Dipolar Nitrones[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,2024,63(14).

Xu, Liren.,Yang, Tilong.,Sun, Hao.,Zeng, Jingwen.,Mu, Shuo.,...&Chen, Gen-Qiang.(2024).Rhodium-Catalyzed Asymmetric Hydrogenation and Transfer Hydrogenation of 1,3-Dipolar Nitrones.ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,63(14).

Xu, Liren,et al."Rhodium-Catalyzed Asymmetric Hydrogenation and Transfer Hydrogenation of 1,3-Dipolar Nitrones".ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 63.14(2024).