Conformational arm-wrestling: Battles for stereochemical control in benzamides bearing matched and mismatched chiral 2- and 6-substituents

Jonathan Clayden*, Yann J Y Foricher, Madeleine Helliwell, Paul Johnson, David Mitjans, Victoria Vinader

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

9 Citations (Scopus)

Abstract

The orientation of a tertiary amide group adjacent to an aromatic ring may be governed by the stereochemistry of an adjacent chiral substituent. With a chiral substituent in both ortho positions, matched/mismatched pairs of isomers result. Evidence for matched stereochemistry is provided by the clean NMR spectra of single conformers, while mismatching gives poor or unexpected selectivities in the formation of chiral substituents, or mixtures of amide conformers. Attempts to use the match-mismatch effect to select for racemic pairs of enantiomeric substituents, and hence develop a "racemate- sequestering" reagent, are described, along with the use of "matching" to scavenge a single enantiomer of a diamine from material of incomplete enantiomeric purity.

Original languageEnglish
Pages (from-to)444-454
Number of pages11
JournalOrganic and Biomolecular Chemistry
Volume4
Issue number3
Early online date23 Nov 2005
DOIs
Publication statusPublished - 7 Feb 2006

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