Likely by accident; possibly by finding globs of crudely smelted copper/tin/lead in the ashes of large bonfires.
Copper is a very nice upgrade from stone for many applications, because it’s basically shatter proof, and it can be beaten back into shape once deformed. Only time it’s not an upgrade is precision slicing implements where sharpness is more important than sturdiness.
So the story was probably something along the lines of
1. Celebrate a successful hunt with a big bonfire.
2. Find globs of ‘stuff’ that weren’t there before while collecting ashes.
3. Try using it for tools and coming to like it (hurts hands less than stone tools)
4. Try recreating it, and discovering where it came from
5. Start experimenting on different rocks, badabing badaboom, ya got metallurgy.
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