syn-Allylstannation of N-Acyliminium Intermediates by Tributyl[gamma-(silyloxy)allyl]stannanes: A Key Reaction for the Diastereoselective Synthesis of Polyhydroxypiperidines and Polyhydroxyazepanes

Floris Chevallier (1) , Alexandre Lumbroso (2) , Isabelle Beaudet (2) , Erwan Le Grognec (2) , Loic Toupet (3) , Jean-Paul Quintard (2)

1 CPM - Chimie et Photonique Moléculaires
2 LSOHOOM - Laboratoire de Synthèse Organique (Hétérochimie organique, organoéléments et matériaux)
3 GMCM - Groupe matière condensée et matériaux

The allylstannation of N-alkenyl N-acyliminium intermediates by tributyl[gamma-(silyloxy)allyl]stannanes afforded the expected adducts with a high syn-selectivity (up to 99: 1). Ensuing ring-closing metathesis afforded dehydropiperidines or dehydroazepanes which were engaged in a stereoselective dihydroxylation reaction leading to polyhydroxypiperidines or polyhydroxyazepanes in good yields. This sequence was applied to a diastereoselective synthesis of (+/-)-1-deoxygulonojirimycine.

Mots clés: Diastereoselectivity; Nitrogen heterocycles; Iminosugars; Tin; Allylation

Domaines: Physique Générale [physics.gen-ph]

Floris Chevallier, Alexandre Lumbroso, Isabelle Beaudet, Erwan Le Grognec, Loic Toupet, et al.. syn-Allylstannation of N-Acyliminium Intermediates by Tributyl[gamma-(silyloxy)allyl]stannanes: A Key Reaction for the Diastereoselective Synthesis of Polyhydroxypiperidines and Polyhydroxyazepanes. European Journal of Organic Chemistry, 2011, 2011 (22), pp.4133-4144. ⟨10.1002/ejoc.201100302⟩. ⟨hal-01068766⟩