P‐Stereogenic Chiral Phosphine−Palladium Complex Catalyzed Enantioselective Synthesis of Phosphoryl‐Substituted Atropisomeric Vinylarenes

• Published in: Advanced synthesis & catalysis Vol. 359; no. 22; pp. 3927 - 3933
• Main Authors: Wu, Hao, Han, Zhengxu S., Qu, Bo, Wang, Dan, Zhang, Yongda, Xu, Yibo, Grinberg, Nelu, Lee, Heewon, Song, Jinhua J., Roschangar, Frank, Wang, Guijun, Senanayake, Chris H.
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 23.11.2017; Wiley Subscription Services, Inc
• Subjects: Aromatic compounds; atropisomeric arenes; axial chirality; Bromides; Catalysis; Chemical synthesis; Chemistry; Chemistry, Applied; Chemistry, Organic; enantioselective catalysis; Grignard reactions; Ligands; P-stereogenic phosphine; Palladium; Phosphines; phosphine−palladium catalysis; Physical Sciences; Science & Technology; phosphine-palladium catalysis; P-stereogenic phosphine; MONOPHOSPHINE LIGANDS; 2+2+2 CYCLOADDITION; C-H ACTIVATION; DYNAMIC KINETIC RESOLUTION; axial chirality; BIARYL NATURAL-PRODUCTS; ASYMMETRIC SUZUKI-MIYAURA; CROSS-COUPLING REACTIONS; ATROPOSELECTIVE SYNTHESIS; atropisomeric arenes; enantioselective catalysis; OXOVANADIUM(IV) COMPLEXES
• ISSN: 1615-4150; 1615-4169
• DOI: 10.1002/adsc.201700837

P‐Stereogenic chiral phosphine BI‐BOP is employed for the first time as ligand to promote catalytic enantioselective synthesis of phosphoryl‐substituted atropisomeric vinylarenes through a palladium−carbene pathway. This strategy utilizes 10 mol% palladium(II) acetate, 10 mol% phosphine ligand as well as a variety of N‐tosylhydrazones and phosphoryl‐substituted aryl bromides as the reaction partners. The desired axially chiral vinylarenes were isolated with up to 80% yield and 96:4 er, and can be further converted effectively and stereoselectively into dialkylphosphoryl‐substituted atropisomeric arenes through a Grignard reaction. This protocol offers a general approach to synthesize phosphoryl‐substituted atropisomeric vinylarenes with high enantiomeric purities.