Depends. Assuming Shaman knows he's going into battle, is primed, and knows his opponent (per forum rules), meaning he knows how fast Supes is (since he gets general knowledge of his opponents, and Supes is a very public superhero), if Shaman can instantly raise shields or slow time at the onset of battle, it's not cut and dry for Supes.
So assuming Shaman comes into battle primed, as per forum rules, and if he were to go to that action depicted in the scan at the onset of battle, meaning he already had his hand on his medicine bag and was in battle posture before the gun, assuming that scan is accurate in that the effects of the magic powder take effect instantly upon the onset of release, could Shaman release it at the word "Go" (simultaneously with the onset of battle)?
If that is the case, I'd give this to Shaman. If he can stop Supes motion at the onset of battle, simultaneously with the implied "Gun" that starts battle, he should be able to take this.
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Superman is faster than thought. Shaman can't win in a straight fight. The speed edge is too great. To beat him, he needs time to pull out his bag of tricks.
If he can actually get some of his uber magic out, then Supes is in deep shit. But he has normal human reactions, AFAIK.
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Supes is faster than normal human thought, that's a given. The issue is, if both are primed to go (per forum rules), both can act simultaneously with the onset of battle, meaning Shaman could likely get off one of his instant magic spells as Supes still has to cover .5 km to strike Shaman, though he'll also do that near instantly as well. It's not a matter of speed of thought as much as it is synching up an instantaneous attack simultaneously with the onset of battle. It's assumed all combatants are battle ready and can act once the gun goes off. Supes is primed to speed blitz and cover the .5 km, Shaman is primed to cast an instantaneous spell.