Conformationally Biased Ketones React Diastereoselectively with Allylmagnesium Halides

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....

Full description

Saved in:
Bibliographic Details
Published in:Journal of organic chemistry 2022-03, Vol.87 (5), p.3042-3065
Main Authors: Bartolo, Nicole D, Demkiw, Krystyna M, Read, Jacquelyne A, Valentín, Elizabeth M, Yang, Yingying, Dillon, Alexandra M, Hu, Chunhua T, Ward, Michael D, Woerpel, K. A
Format: Article
Language:English
Subjects:
Indicators and Reagents
Ketones - chemistry
Molecular Conformation
Stereoisomerism
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary: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.
ISSN:0022-3263
1520-6904
1520-6904
DOI:10.1021/acs.joc.1c02844