Every Targetmaster and Headmaster toy has appeared in some form of G1 canon...

Targetmasters
Artfire = appeared in manga
Blurr = appeared in cartoon and comics
Crosshairs = appeared in animé, cartoon, manga and comics
Cyclonus = appeared in cartoon and comics
Hot Rod = appeared in cartoon and comics
Kup = appeared in cartoon and comics
Landfill = appeared in comics
Misfire = appeared in animé, cartoon, manga and comics
Needlenose = appeared in comics
Pointblank = appeared in animé, cartoon, manga and comics
Quake = appeared in comics
Quickmix = appeared in comics
Scoop = appeared in comics
Scourge = appeared in cartoon and comics
Sluglslinger = appeared in animé, cartoon, manga and comics
Spinister = appeared in comics
Stepper = appeared in manga
Sureshot = appeared in animé, cartoon, manga and comics
Triggerhappy = appeared in animé, cartoon, manga and comics

Headmasters
Apeface = appeared in animé, cartoon, manga and comics
Brainstorm = appeared in animé, cartoon, manga and comics
Bullhorn = appeared in animé and manga
Cab = appeared in animé and manga
Cancer = appeared in animé and manga
Chromedome = appeared in animé, cartoon, manga and comics
Fangry = appeared in comics
Fortress Maximus = appeared in animé, cartoon, manga and comics
Goshooter = appeared in animé and manga
Hardhead = appeared in animé, cartoon, manga and comics
Highbrow = appeared in animé, cartoon, manga and comics
Horri-Bull = appeared in comics
Hosehead = appeared in comics
Minerva = appeared in animé and manga
Mindwipe = appeared in animé, cartoon, manga and comics
Nightbeat = appeared in comics
Scorponok = appeared in animé, cartoon, manga and comics
Siren = appeared in comics
Skullcruncher = appeared in animé, cartoon, manga and comics
Snapdragon = appeared in animé, cartoon, manga and comics
Squeezeplay = appeared in comics
Weirdwolf = appeared in animé, cartoon, manga and comics
Wilder = appeared in animé and manga

Headmaster Warriors
Kirk = appeared in animé and manga
Loafer = appeared in animé and manga
Lioné = appeared in animé and manga
Rodney = appeared in animé and manga
Shuffler = appeared in animé and manga
Trizer = appeared in animé and manga

*Blurr, Hot Rod/Rodimus Prime, Kup, Cyclonus and Scourge appeared in the animé but never as Targetmasters.
**Arcee appeared as a Headmaster (binary bonded to Daniel Witwicky) in the cartoon only. Sunstreaker appeared as a Headmaster (binary bonded to Hunter O'Nion) in the IDW comics only. No official toys of either of these Headmasters have been made.
-------------
References
http://tfwiki.net/wiki/Targetmaster
http://tfwiki.net/wiki/Headmaster_(technology)
http://tfwiki.net/wiki/Headmaster_Warrior