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Updated: Oct 5, 2025

A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species
Published on: August 16, 2018
Origin of High Diastereoselectivity in Reactions of Seven-Membered-Ring Enolates
Olga Lavinda1, Collin H Witt1, K A Woerpel1
1Department of Chemistry, New York University, 100 Washington Square East, New York, NY 10003, USA.
Abstract:
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.
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