Additions of Organomagnesium Halides to α-Alkoxy Ketones: Revision of the Chelation-Control Model

Jacquelyne A. Read; Yingying Yang; K. A. Woerpel

doi:10.1021/acs.orglett.7b01161

Additions of Organomagnesium Halides to α-Alkoxy Ketones: Revision of the Chelation-Control Model

Jacquelyne A. Read, Yingying Yang, K. A. Woerpel

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

The chelation-control model explains the high diastereoselectivity obtained in additions of organometallic nucleophiles to α-alkoxy ketones but fails for reactions of allylmagnesium halides. Low diastereoselectivity in ethereal solvents results from no chelation-induced rate acceleration. Additions of allylmagnesium bromide to carbonyl compounds are diastereoselective using CH₂Cl₂ as the solvent even though rate acceleration is still absent. Stereoselectivity likely arises from the predominance of the chelated form in solution. Therefore, a revised chelation-control model is proposed.

Original language	English (US)
Pages (from-to)	3346-3349
Number of pages	4
Journal	Organic Letters
Volume	19
Issue number	13
DOIs	https://doi.org/10.1021/acs.orglett.7b01161
State	Published - Jul 7 2017

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry

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abstract = "The chelation-control model explains the high diastereoselectivity obtained in additions of organometallic nucleophiles to α-alkoxy ketones but fails for reactions of allylmagnesium halides. Low diastereoselectivity in ethereal solvents results from no chelation-induced rate acceleration. Additions of allylmagnesium bromide to carbonyl compounds are diastereoselective using CH2Cl2 as the solvent even though rate acceleration is still absent. Stereoselectivity likely arises from the predominance of the chelated form in solution. Therefore, a revised chelation-control model is proposed.",

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AB - The chelation-control model explains the high diastereoselectivity obtained in additions of organometallic nucleophiles to α-alkoxy ketones but fails for reactions of allylmagnesium halides. Low diastereoselectivity in ethereal solvents results from no chelation-induced rate acceleration. Additions of allylmagnesium bromide to carbonyl compounds are diastereoselective using CH2Cl2 as the solvent even though rate acceleration is still absent. Stereoselectivity likely arises from the predominance of the chelated form in solution. Therefore, a revised chelation-control model is proposed.

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Additions of Organomagnesium Halides to α-Alkoxy Ketones: Revision of the Chelation-Control Model

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