biostudies-literatureVidal LDivision of ChemistryUniversity of Liverpool8503-8508https://www.ebi.ac.uk/biostudies/studies/S-EPMC9706811biostudies-literatureUnknown24(46)Enantioselective cyclopropanation of α-carbonyl sulfoxonium ylides (SY) has so far been limited to addition/ring closure reactions on electron-poor olefins. Herein, we report the iridium-catalyzed intramolecular cyclopropanation of SY in the presence of a chiral diene in up to 96% yield and 98% enantioselectivity. Moreover, density functional theory calculations suggest that the <i>re</i> face of the olefin preferably attacks an iridium carbene intermediate in an asynchronous concerted step that is independent of the geometry of the olefin.Organic lettersEnantioselective Intramolecular Iridium-Catalyzed Cyclopropanation of α-Carbonyl Sulfoxonium Ylides.PMC9706811CHE-1764328Aissa CHackett ARobertson CMChen PPHouk KNVidal LNicolas EfalseEnantioselective Intramolecular Iridium-Catalyzed Cyclopropanation of α-Carbonyl Sulfoxonium Ylides.Enantioselective cyclopropanation of α-carbonyl sulfoxonium ylides (SY) has so far been limited to addition/ring closure reactions on electron-poor olefins. Herein, we report the iridium-catalyzed intramolecular cyclopropanation of SY in the presence of a chiral diene in up to 96% yield and 98% enantioselectivity. Moreover, density functional theory calculations suggest that the <i>re</i> face of the olefin preferably attacks an iridium carbene intermediate in an asynchronous concerted step that is independent of the geometry of the olefin.2022-01-01T00:00:00Z2022 Nov2025-04-05T09:43:38.934Z2025-04-05T09:43:38.934ZS-EPMC97068113636797010.1021/acs.orglett.2c03396