Kinetic and thermodynamic stereocontrol in the atroposelective formation of sulfoxides by oxidation of 2-sulfanyl-1-naphthamides

Mark S. Betson, Jonathan Clayden*, Madeleine Helliwell, David Mitjans

*Corresponding author for this work

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

17 Citations (Scopus)

Abstract

Atropisomeric aromatic amides bearing 2-sulfanyl groups are oxidised by m-CPBA to the corresponding sulfoxides apparently with very high diastereoselectivity. NMR studies and oxidations of chiral benzamides however indicate that the kinetic selectivity of the oxidation is in fact relatively poor, and that the final diastereoisomeric ratio (typically >99:1) is under thermodynamic control, with relatively unhindered Ar-CO rotation readily converting the less stable to the more stable product diastereoisomer. Molecular mechanics indicates that the thermodynamic diastereoselectivity results principally from electrostatic repulsion between the C=O and S-O dipoles.

Original languageEnglish
Pages (from-to)3898-3904
Number of pages7
JournalOrganic and Biomolecular Chemistry
Volume3
Issue number21
Early online date7 Sep 2005
DOIs
Publication statusPublished - 7 Nov 2005

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