Enantioselective Synthesis of Deoxymannojirimycin Based on Sharpless Asymmetric Epoxidation of a Highly Functionalized Allylic Alcohol

Marie-Céline Lamas, Max Malacria, Serge Thorimbert
  • European Journal of Organic Chemistry, March 2011, Wiley
  • DOI: 10.1002/ejoc.201100102

What is it about?

An efficient enantioselective synthesis of deoxymannojirimicin is reported. It is based on the unusual Sharpless asymmetric epoxidation of a silyl-substituted allylic 1,4-amino alcohol coupled with a further highly stereoselective intra-molecular aldolization. Both enantiomers of deoxymannojirimicin are available. An orthogonally protected polyhydroxylated piperidine was prepared, which could formally lead to other members of this piperidine family.


Professor Serge THORIMBERT
Sorbonne Université

This publication has been cited and highlighted by M. M. Heravi et al in his review (Applications of Sharpless asymmetric epoxidation in total synthesis. Tetrahedron : Asymmetry 2015, 154, 405-495. … « It is worthwhile to discuss this specific Sharpless asymmetric epoxidation strategy regarding its precursor in more detail. Notably, the Sharpless asymmetric epoxidation of alkenes bearing both amine and alcohol functions in the allylic positions have largely been overlooked, probably due to challenging substrates. … Since precursor 72 has a double bond bearing three substituents, it can be considered to be relatively hindered and more challenging and tedious conditions are expected. However, the reaction occurred and gave an average yield of 80% upon purification. Under the optimal conditions using (+)-DIPT, an enantiomeric ratio (er) of 98:2 was observed for (+)-73. »

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