Metzenbaum's claim that John Glenn never had a real job probably ranks pretty high.
A lot of politicians have gone that route, usually when the target is a career politician/government employee.
In 2010, Bill White sounded almost Romney-esque when he said Rick Perry had never had a real job and that his lack of private sector experience disqualified him from public office (which already sounds illogical on its face, but was made worse by the fact that Perry's non-government jobs were in the unimpeachable fields of military service and working on the family farm).