No. Creatures on the stack are still "spells". You can cast that lightning bolt, but if a creature is on the stack you can't choose it as a target.
509.2. Second, for each attacking creature that's become blocked, the active player announces that creature's damage assignment order, which consists of the creatures blocking it in an order of that player's choice. (During the combat damage step, an attacking creature can't assign combat damage to a creature that's blocking it unless each creature ahead of that blocking creature in its order is assigned lethal damage.) This turn-based action doesn't use the stack.Example: Vastwood Gorger is blocked by Llanowar Elves, Runeclaw Bear, and Serra Angel. Vastwood Gorger's controller announces the Vastwood Gorger's damage assignment order as Serra Angel, then Llanowar Elves, then Runeclaw Bear.