Sulfoxides as 'traceless' resolving agents for the synthesis of atropisomers by dynamic or classical resolution

Jonathan Clayden*, Przemyslaw M. Kubinski, Federica Sammiceli, Madeleine Helliwell, Louis Diorazio

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)

40 Citations (Scopus)

Abstract

Reacting (-)-menthyl sulfinate with an atropisomeric but racemic aryllithium gives two atropdiastereoisomeric sulfoxides. Separation (by chromatography or crystallisation) and sulfoxide-lithium exchange of each diastereoisomer regenerates the aryllithium in enantiomerically pure form which can be quenched with a range of electrophiles with retention of stereochemical integrity. Overall the reaction sequence is a resolution but without the need for an acidic or basic substituent - a 'traceless' method. In certain instances, for example when the nucleophile is an ortholithiated peri-substituted 1-naphthamide, the diastereoisomeric sulfoxides may be interconverted thermally. This allows a dynamic resolution, under thermodynamic control, and hence in principle can give yields of the final products of greater than 50%. The utility of the method is demonstrated by the synthesis of a known atropisomeric phosphine ligand.

Original languageEnglish
Pages (from-to)4387-4397
Number of pages11
JournalTetrahedron
Volume60
Issue number20
Early online date25 Feb 2004
DOIs
Publication statusPublished - 10 May 2004

Keywords

  • Atropisomers
  • Binaphthyls
  • Resolution
  • Sulfoxides

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