Ammonium-Directed Oxidation of Cyclic Allylic and Homoallylic Amines

Christopher W. Bond, Alexander J. Cresswell, Stephen G. Davies, Ai M. Fletcher, Wataru Kurosawa, James A. Lee, Paul M. Roberts, Angela J. Russell, Andrew D. Smith, James E. Thomson

Research output: Contribution to journalArticlepeer-review

Abstract

The ammonium-directed olefinic oxidation of a range of cyclic allylic and homoallylic amines has been investigated. Functionalization of a range of allylic 3-(N,N-dibenzylamino)cycloalk-1-enes with m-CPBA in the presence of Cl3CCO2H gives exclusively the corresponding syn-epoxide for the 5-membered ring (> 99:1 dr), the anti-epoxide for the 8-membered ring (>99:1 dr), and predominantly the anti-epoxide for the 7-membered ring (94:6 dr). Oxidation of the homoallylic amines 3-(N-benzylamino)methylcyclohex-1-ene and 3-(N,N-dibenzylamino)methylcyclohex-1-ene gave, in both cases, the corresponding N-protected 1,2-anti-2,3-syn-3-aminomethylcyclohexane-1,2-diol with high levels of diastereoselectivity (>= 90:10 dr). The versatile synthetic intermediates resulting from these oxidation reactions are readily transformed into a range of amino diols.

Original languageEnglish
Pages (from-to)6735-6748
Number of pages14
JournalThe Journal of Organic Chemistry
Volume74
Issue number17
DOIs
Publication statusPublished - 4 Sept 2009

Keywords

  • HOMOCHIRAL ALPHA,BETA-UNSATURATED ESTERS
  • DIASTEREOSELECTIVE CONJUGATE ADDITION
  • ASYMMETRIC-SYNTHESIS
  • TRANSITION-STATE
  • EPOXIDE REACTIONS
  • LITHIUM AMIDES
  • PEROXY-ACIDS
  • ALCOHOLS
  • DIHYDROXYLATION
  • CIS

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