Copper‐Catalyzed Asymmetric Synthesis of Silicon‐Stereogenic Benzoxasiloles

• Published in: Angewandte Chemie International Edition Vol. 63; no. 7; pp. e202317973 - n/a
• Main Authors: Gan, Wan‐Er, Wu, Yong‐Shun, Wu, Bin, Fang, Chun‐Yuan, Cao, Jian, Xu, Zheng, Xu, Li‐Wen
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 12.02.2024; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Asymmetric Catalysis; Asymmetric synthesis; Asymmetry; Benzoxasilole; Chemical synthesis; Chemistry; Chemistry, Multidisciplinary; Copper; Copper Catalysis; Enantiomers; Physical Sciences; Reagents; Science & Technology; Silane; Silanes; Silicon; Silicon-Stereogenic; NICKEL-COMPLEXES; ACTIVATION; ENANTIOSELECTIVE SILYLATION; STEREOCHEMISTRY; HYDROSILYLATION; ANION RELAY CHEMISTRY; CROSS-COUPLING REACTIONS; Asymmetric Catalysis; Benzoxasilole; ISOSTERES; ARYL; Copper Catalysis; LIGAND; Silicon-Stereogenic; Silane; silicon-stereogenic; Cu-catalysis; benzoxasilole; silane; Asymmetric catalysis
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202317973

A Cu‐catalyzed asymmetric synthesis of silicon‐stereogenic benzoxasiloles has been realized via intramolecular Si−O coupling of [2‐(hydroxymethyl)phenyl]silanes. Cu(I)/difluorphos is found to be an efficient catalytic system for enantioselective Si−C bond cleavage and Si−O bond formation. In addition, kinetic resolution of racemic substituted [2‐(hydroxymethyl)phenyl]silanes using Cu(I)/ PyrOx (pyridine‐oxazoline ligands) as the catalytic system is developed to afford carbon‐ and silicon‐stereogenic benzoxasiloles. Ring‐opening reactions of chiral benzoxasiloles with organolithiums and Grignard reagents yield various enantioenriched functionalized tetraorganosilanes. A Cu‐catalyzed asymmetric synthesis of silicon‐stereogenic benzoxasiloles has been realized via the intramolecular Si−O coupling of [2‐(hydroxymethyl)phenyl]silanes using Cu(I)/difluorphos as the efficient catalytic system. Kinetic resolution of racemic substituted [2‐(hydroxymethyl)phenyl]silanes using Cu(I)/PyrOx as the catalytic system was also achieved to afford carbon‐ and silicon‐stereogenic benzoxasilole species.