Depends on class and current stats.
For sheild wearers, you want mastery for that big bonus to block. Once parry, dodge, and block adds up to 102.4% stack mastery first, then try to gem, reforge, and enchant your gear so that Dodge and parry equal the same, as these stats have diminishing returns.
Pallies and Warriors have different talents and skills to help with aggro so rely on this and focus you gear towards the 102.4% damage mitigation.
Deathknights I am not too sure on, but I think they have a talent that bulks up stam. I believe thats their big stat.
Bears... no clue lol
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