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- Title
Rhodium‐Catalyzed Asymmetric Hydrogenation and Transfer Hydrogenation of 1,3‐Dipolar Nitrones.
- Authors
Xu, Liren; Yang, Tilong; Sun, Hao; Zeng, Jingwen; Mu, Shuo; Zhang, Xumu; Chen, Gen‐Qiang
- Abstract
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.
- Subjects
NITRONES; HYDROGENATION; CATALYTIC hydrogenation; SCISSION (Chemistry); TRANSFER hydrogenation; RHODIUM
- Publication
Angewandte Chemie, 2024, Vol 136, Issue 14, p1
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.202319662