Abstract: | Norbornene derivatives with one or two carbonyl-containing substituents at positions 5 and 6 (anhydrides, esters, amides, cyclic ketones) undergo an electron impact induced rerro-Diels-Alder fragmentation accompanied by the migration of one hydrogen atom (RDA + H) giving rise to the dienophile + H]+ ions. Bicyclo2.2.2]octene derivatives substituted at C(5) and C(6) by a ring with two carbonyl groups (anhydrides, imides, diketones) undergo an RDA fragmentation accompanied by the transfer of two hydrogen atoms (RDA + 2H). Bicyclo2.2.2]octene 5,6-diesters undergo both the RDA + H and RDA + 2H fragmentations, and the relative abundance of the resulting dienophile + H]+ and dienophile + 2H]+˙ ions is strongly affected by configuration. |