Captain Kirk: James T. Kirk was awarded the captaincy of the U.S.S. Enterprise at the young age of 31, and famously commanded her on her five-year exploratory mission, encountering many new species and civilizations.
Khan: Khan Nonnien Singh was a genetically engineered Augment who ruled a large region of late-20th-century Earth. During the Eugenics Wars, he and other Augments fled Earth and were found by the Enterprise.