biostudies-literatureLavinda ODivision of ChemistryFoundation for the National Institutes of HealthNational Institute of General Medical SciencesNIH HHSNIGMS NIH HHSe202114183https://www.ebi.ac.uk/biostudies/studies/S-EPMC8940697biostudies-literatureUnknown61(14)Unlike many reactions of their six-membered-ring counterparts, the reactions of chiral seven-membered-ring enolates are highly diastereoselective. Diastereoselectivity was observed for a range of substrates, including lactam, lactone, and cyclic ketone derivatives. The stereoselectivity arises from torsional and steric interactions that develop when electrophiles approach the diastereotopic π-faces of the enolates, which are distinguished by subtle differences in the orientation of nearby atoms of the ring.Angewandte Chemie (International ed. in English)Origin of High Diastereoselectivity in Reactions of Seven-Membered-Ring Enolates.PMC8940697CHE-01162222S10-OD016343S10 OD016343R01 GM1292861R01GM129286Witt CHWoerpel KALavinda OfalseOrigin of High Diastereoselectivity in Reactions of Seven-Membered-Ring Enolates.Unlike many reactions of their six-membered-ring counterparts, the reactions of chiral seven-membered-ring enolates are highly diastereoselective. Diastereoselectivity was observed for a range of substrates, including lactam, lactone, and cyclic ketone derivatives. The stereoselectivity arises from torsional and steric interactions that develop when electrophiles approach the diastereotopic π-faces of the enolates, which are distinguished by subtle differences in the orientation of nearby atoms of the ring.2022-01-01T00:00:00Z2022 Mar2025-04-21T14:19:24.775Z2025-04-21T14:19:24.775ZS-EPMC89406973507697810.1002/anie.202114183