I am particularly curious about Norman Osborn.
Any universe is fine, as long as you state about which universe you are answering for.
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The Norman Osborn in the Ultimate Universe (1610) is listed as having a "PhD in various sciences" on Marvel's own site. He is certainly portrayed as having a direct hand in the Oz Formula that causes both his and Spider-Man's powers, although still seems to be portrayed mostly as an industrialist/CEO rather than as a scientist.
Jackal, the Spider-Man villain behind the notorious "Clone Saga," was a professor of biochemistry and has a PhD according to Wikipedia.
There is Professor Smythe, the robotics and arachnid physiology expert, who built the "spider slayer" robots to hunt Spider-Man (including one that was large for him to ride inside it and pilot it). He first appeared in The Amazing Spider-Man no. 25, and he usually worked in collaboration with J. Jonah Jameson, up through his death in issue no. 191.