Palladium‐Catalyzed Asymmetric Hydrogenolysis of Aryl Triflates for Construction of Axially Chiral Biaryls

• Published in: Angewandte Chemie International Edition Vol. 62; no. 16; pp. e202301337 - n/a
• Main Authors: Li, Xiang, Wang, Gao‐Wei, Liu, Li‐Xia, Yu, Chang‐Bin, Zhou, Yong‐Gui
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 11.04.2023; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Alkylation; Aromatic compounds; Aryl Triflates; Asymmetric Hydrogenolysis; Asymmetry; Axially Chiral Biaryls; Chemistry; Chemistry, Multidisciplinary; Desymmetrization; Hydrogenolysis; Palladium; Physical Sciences; Science & Technology; HYDROGENATION; Axially Chiral Biaryls; ENANTIOSELECTIVE SYNTHESIS; NATURAL-PRODUCTS; Desymmetrization; ALLYLIC ALKYLATION; ATROPISOMERIC BIARYLS; Palladium; Asymmetric Hydrogenolysis; NICKEL; Aryl Triflates; KINETIC RESOLUTION; CYCLIC DIARYLIODONIUM; ATROPOSELECTIVE SYNTHESIS; DERIVATIVES
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202301337

Here we report the first palladium‐catalyzed asymmetric hydrogenolysis of readily available aryl triflates via desymmetrization and kinetic resolution for facile construction of axially chiral biaryl scaffolds with excellent enantioselectivities and s selectivity factors. The axially chiral monophosphine ligands could be prepared from these chiral biaryl compounds and were further applied to palladium‐catalyzed asymmetric allylic alkylation with excellent ee values and high branched and linear ratio, which demonstrated the potential utility of this methodology. We have developed the first palladium‐catalyzed asymmetric hydrogenolysis of aryl triflates through desymmetrization and kinetic resolution that allows the facile construction of axially chiral biaryl scaffolds with excellent results. These chiral compounds could be further converted into chiral monophosphine ligands, which were then used in asymmetric allylic alkylation to produce the desired product with high regio‐ and enantioselectivities.