Venus #1
Black Knight/Yellow Claw
Atlas Era Heroes #1, #2, #3
Daring Mystery #1, #2
Mystic Comics #1
Golden Age Human Torch #1
Golden Age Sub-Mariner #1 

As you can see all are from the Golden/Atlas age, and these are the Masterworks I primarily purchase - almost exclusively actually over the past 20 years or so after a run of Silver Age titles. I'm much more interested in seeing stuff brand-new and in some cases, never before reprinted than stuff often available in other formats. I did spring for Ka-Zar #1 at the start of this year though.