Evidence for an Olefinic Intermediate in the Configurational Inversion Accompanying Hydrogenolysis of a 7-Oxanorbornyl Vicinal Dibromide

Article abstract of DOI:10.1016/0040-4039(94)85227-8

The endo,endo-2,3-dibromo-7-oxanorborneno<2,3-c>succinimide (1) undergoes complete inversion upon hydrogenolysis of the bromine substituents to form (5) (Zn/Ag couple in THF) or (26) (H2, Pd/C).The highly reactive dienophile, N-methyl 7-oxanorbornadieno<2,3-c>maleimide (3) is shown to be a transient intermediates in the Zn/Ag couple experiments by trapping with furan.Deuterium labelling experiments have been used to help elucidate the mechanism of these reactions.