Organocatalytic Asymmetric Synthesis of Si-Stereogenic Silyl Ethers

• Published in: Journal of the American Chemical Society Vol. 144; no. 23; pp. 10156 - 10161
• Main Authors: Zhou, Hui, Han, Jung Tae, Nöthling, Nils, Lindner, Monika M., Jenniches, Judith, Kühn, Clemens, Tsuji, Nobuya, Zhang, Li, List, Benjamin
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 15.06.2022; Amer Chemical Soc
• Subjects: Carbon; Chemistry; Chemistry, Multidisciplinary; Communication; Ethers - chemical synthesis; Physical Sciences; Science & Technology; Silicon; Stereoisomerism; CATALYSIS; COMPLEX; MECHANISM; SILANES; SILICON; CONSTRUCTION; STEREOCHEMISTRY; CONFIGURATION; ALDOLIZATIONS; DESYMMETRIZATION
• ISSN: 0002-7863; 1520-5126; 1520-5126
• DOI: 10.1021/jacs.2c04261

Functionalized enantiopure organosilanes are important building blocks with applications in various fields of chemistry; nevertheless, asymmetric synthetic methods for their preparation are rare. Here we report the first organocatalytic enantioselective synthesis of tertiary silyl ethers possessing “central chirality” on silicon. The reaction proceeds via a desymmetrizing carbon–carbon bond forming silicon–hydrogen exchange reaction of symmetrical bis­(methallyl)­silanes with phenols using newly developed imidodiphosphorimidate (IDPi) catalysts. A variety of enantiopure silyl ethers was obtained in high yields with good chemo- and enantioselectivities and could be readily derivatized to several useful chiral silicon compounds, leveraging the olefin functionality and the leaving group nature of the phenoxy substituent.