biostudies-literatureZhou HEuropean Research CouncilDeutsche ForschungsgemeinschaftMinistry of Education, Culture, Sports, Science and TechnologyJapan Society for the Promotion of Science10156-10161https://www.ebi.ac.uk/biostudies/studies/S-EPMC9490845biostudies-literatureUnknown144(23)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 Journal of the American Chemical SocietyOrganocatalytic Asymmetric Synthesis of Si-Stereogenic Silyl Ethers.PMC9490845EXC 2033390677874RESOL20K2251521H01925694228Lindner MMHan JTTsuji NNothling NZhang LZhou HList BJenniches JKuhn CfalseOrganocatalytic Asymmetric Synthesis of Si-Stereogenic Silyl Ethers.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 2022-01-01T00:00:00Z2022 Jun2025-04-25T19:11:51.493Z2025-04-06T07:50:31.838ZS-EPMC94908453564927010.1021/jacs.2c04261