Stereodivergent synthesis of iminosugars from stannylated derivatives of (S)-vinylglycinol.

Alexandre Lumbroso (1) , Isabelle Beaudet (1) , Loïc Toupet (2) , Erwan Le Grognec (1) , Jean-Paul Quintard (1)

1 LSOHOOM - Laboratoire de Synthèse Organique (Hétérochimie organique, organoéléments et matériaux)
2 IPR - Institut de Physique de Rennes

An original access to iminosugars from a cis/trans mixture of stannylated oxazolidinones 5 is reported. The dehydropiperidines 7-trans and 7-cis were obtained stereoselectively with an RS and SS configuration depending on the order of the Sn-Li transmetalation (followed by electrophilic trapping) and of the ring closing metathesis reactions due to the stereoselective epimerization of the α-aminoanion intermediate. The dehydropiperidines 7-trans and 7-cis were subsequently used for the synthesis of enantiopure homonojirimycin analogs.

Mots clés: IMINOSUGAR C-GLYCOSIDES; TIN-LITHIUM EXCHANGE; THERAPEUTIC APPLICATIONS; LYSOSOMAL STORAGE DISORDERS; SINGLE CHIRAL CYANOHYDRIN; RING-CLOSING METATHESIS; NATURAL OCCURRENCE; ALPHA; INHIBITION; NITROGEN

Domaines: Chimie organique

Alexandre Lumbroso, Isabelle Beaudet, Loïc Toupet, Erwan Le Grognec, Jean-Paul Quintard. Stereodivergent synthesis of iminosugars from stannylated derivatives of (S)-vinylglycinol.. Organic Letters, 2013, 15 (1), pp.160-3. ⟨10.1021/ol303213r⟩. ⟨hal-00805880⟩