Conformationally Biased Ketones React Diastereoselectively with Allylmagnesium Halides

Nicole D. Bartolo, Krystyna M. Demkiw, Jacquelyne A. Read, Elizabeth M. Valentín, Yingying Yang, Alexandra M. Dillon, Chunhua T. Hu, Michael D. Ward, K. A. Woerpel

Research output: Contribution to journalArticlepeer-review


The addition of the highly reactive reagent allylmagnesium halide to α-substituted acyclic chiral ketones proceeded with high stereoselectivity. The stereoselectivity cannot be analyzed by conventional stereochemical models because these reactions do not conform to the requirements of those models. Instead, the stereoselectivity arises from the approach of the nucleophile to the most accessible diastereofaces of the lowest-energy conformations of the ketones. High stereoselectivity is expected, and the stereochemical outcome can be predicted, with conformationally biased ketones that have sterically distinguishable diastereofaces wherein only one face is accessible for nucleophilic addition. The conformations of the ketones can be determined by a combination of computational modeling and, in some cases, structure determination by X-ray crystallography.

Original languageEnglish (US)
Pages (from-to)3042-3065
Number of pages24
JournalJournal of Organic Chemistry
Issue number5
StatePublished - Mar 4 2022

ASJC Scopus subject areas

  • Organic Chemistry


Dive into the research topics of 'Conformationally Biased Ketones React Diastereoselectively with Allylmagnesium Halides'. Together they form a unique fingerprint.

Cite this