The correct order of key events regarding the exploration of space, beginning with the earliest, is:
first humans in space, first humans on the moon, first space shuttle flights.
Thus, the option would be:
first humans in space, first space shuttle flights, first humans on the moon.
(Note: The correct phrasing in the answer construction should start with "first humans in space" leading to "first humans on the moon," followed by "first space shuttle flights," making it chronologically accurate.)