Cyclododecatetraene tetraepoxide: highly diastereofacial epoxidation of all-(Z)-1,4,7,10-cyclododecatetraene and selective synthesis of bridged bis-oxocanes

Sophie Guiard; Michel Giorgi; Maurice Santelli; Jean-Luc Parrain

doi:10.1021/jo026736r

Cyclododecatetraene tetraepoxide: highly diastereofacial epoxidation of all-(Z)-1,4,7,10-cyclododecatetraene and selective synthesis of bridged bis-oxocanes

J Org Chem. 2003 Apr 18;68(8):3319-22. doi: 10.1021/jo026736r.

Authors

Sophie Guiard¹, Michel Giorgi, Maurice Santelli, Jean-Luc Parrain

Affiliation

¹ Laboratoire de Synthèse Organique, UMR CNRS 6009, Faculté des Sciences de Saint Jérôme, Avenue Esc Normandie-Niemen, F-13397 Marseille Cedex 20, France.

PMID: 12688811
DOI: 10.1021/jo026736r

Abstract

Epoxidation of all-(Z)-1,4,7,10-cyclododecatetraene has been investigated with use of m-CPBA and dimethyldioxirane in anhydrous solvent. The diastereoselectivity of multiple epoxidation steps is complete affording only exo,exo,exo,endo-1,4,7,10-tetraepoxide. To understand this result, the step-by-step epoxidation reaction was investigated and each step was found to be highly regio- and stereoselective. Finally, a Lewis acid-catalyzed ethanolysis or treatment with HBr/KBr of the tetraepoxide gave rearranged diepoxy-oxabicyclo[5.5.1]tridecane (bridged bis-oxocanes) in which eight stereocenters were controlled.