Abstract

AbstractUnlike 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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