Enantioselective construction of six- and seven-membered triorgano-substituted silicon-stereogenic heterocycles

• Published in: Nature communications Vol. 12; no. 1; pp. 1249 - 9
• Main Authors: Chen, Shuyou, Mu, Delong, Mai, Pei-Lin, Ke, Jie, Li, Yingzi, He, Chuan
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 23.02.2021; Nature Publishing Group; Nature Portfolio
• Subjects: 140/131; 140/58; 639/638/403/933; 639/638/403/935; 639/638/77/883; 639/638/77/888; Catalysis; Chemical synthesis; Chirality; Dehydrogenation; Enantiomers; Fluorescence; Functional materials; Humanities and Social Sciences; multidisciplinary; Optoelectronics; Rhodium; Science; Science (multidisciplinary); Silicon; Silicon compounds; Substitutes
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-021-21489-6

The exploitation of chirality at silicon in asymmetric catalysis is one of the most intriguing and challenging tasks in synthetic chemistry. In particular, construction of enantioenriched mediem-sized silicon-stereogenic heterocycles is highly attractive, given the increasing demand for the synthesis of novel functional-materials-oriented silicon-bridged compounds. Here, we report a rhodium-catalyzed enantioselective construction of six- and seven-membered triorgano-substituted silicon-stereogenic heterocycles. This process undergoes a direct dehydrogenative C−H silylation, giving access to a wide range of triorgano-substituted silicon-stereogenic heterocycles in good to excellent yields and enantioselectivities, that significantly enlarge the chemical space of the silicon-centered chiral molecules. Further elaboration of the chiral monohydrosilane product delivers various corresponding tetraorgano-substituted silicon-stereogenic heterocycles without the loss of enantiopurity. These silicon-bridged heterocycles exhibit bright blue fluorescence, which would have potential application prospects in organic optoelectronic materials. Enantioenriched medium-sized silicon-stereogenic heterocycles are in high demand due to the potential use in functional materials. Here, the authors show a rhodium-catalyzed enantioselective synthesis of six- and seven-membered tri-organosubstituted silicon-stereogenic heterocycles.