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 language | English |
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Pages (from-to) | 6735-6748 |
Number of pages | 14 |
Journal | The Journal of Organic Chemistry |
Volume | 74 |
Issue number | 17 |
DOIs | |
Publication status | Published - 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