Details

Autor(en) / Beteiligte

• Gou, Xue‐Ya
• Li, Yuke
• Shi, Wei‐Yu
• Luan, Yu‐Yong
• Ding, Ya‐Nan
• An, Yang
• Huang, Yan‐Chong
• Zhang, Bo‐Sheng
• Liu, Xue‐Yuan
• Liang, Yong‐Min

Titel

Ruthenium‐Catalyzed Stereo‐ and Site‐Selective ortho‐ and meta‐C−H Glycosylation and Mechanistic Studies

Ist Teil von

• Angewandte Chemie International Edition, 2022-08, Vol.61 (32), p.e202205656-n/a

Auflage

International ed. in English

Ort / Verlag

Germany: Wiley Subscription Services, Inc

Erscheinungsjahr

2022

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• C‐aryl glycosides are popular basic skeletons in biochemistry and pharmaceutical chemistry. Herein, ruthenium‐catalyzed highly stereo‐ and site‐selective ortho‐ and meta‐CAr−H glycosylation is described. A series of C‐aryl pyranosides and furanosides were synthesized by this method. The strategy showed good substrate scope, and various N‐heterocyclic directing groups were compatible with the reaction system. A mechanistic study suggested that the key pathway of ortho‐CAr−H glycosylation might involve oxidative addition/reduction elimination, whereas aryl meta‐C−H glycosylation was mediated by σ‐activation. Density functional theory calculations also showed that the high stereoselectivity of meta‐CAr−H glycosylation was due to steric hindrance. A series of C‐aryl pyranosides and furanosides were synthesized by ruthenium‐catalyzed ortho‐ and meta‐CAr−H glycosylation. Mechanistic studies suggest that the key pathway of ortho‐CAr−H glycosylation involves an oxidative addition/reductive elimination process, while aryl meta‐C−H glycosylation is mediated by σ‐activation. DFT calculations showed that steric hindrance is responsible for the high stereoselectivity of meta‐CAr−H glycosylation.