Which of the non-rake natural attacks does a big cat still get while in a grapple? Grapple rules state that actions requiring two hands can't be taken, so would that mean that all the cat loses is one of its front claw attacks?
So if it's being grappled it can use all three since none of their attacks require two hands to do.
If they are the one grappling they get 0 and instead do a grapple check and then can choose damage with a natural attack.
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Big cats (if you mean the druid companion) have a rake attack that is activate when they start a turn grappling a target and they successful make a grappling attack during their turn.
So:
round 1, no grapple, full attack adjacent to the target: 3 attacks plus a free grappling attempt if they hit;
round 2, the turn start with the big cat grappling a target. At that point, if it want to maintain the grapple it make a grappling check. It the check succeed it get one of its normal attacks (it can choose between bite or claw) and then it can make 2 rake attacks. If it fail it get none, as grappling is a standard action.
Edit: reading the description of the big cat AC, it say rake and the damage, so apparently only 1 rake attack, while the lion and tiger entry in the bestiary list rake (2 claws ...) and the appropriate attack bonus and damage. I think it is a simple error and the big cats AC are meant to have 2 rake attacks, but I am a cat lover.
If it is in a grapple because of Grab, it deals the damage of whatever weapon triggered the grab ability to start the grapple.
If, like, someone grappled Tigger, and then Tigger gained control of the grapple, and then decided to deal damage: He does unarmed strike damage.
The cat will never need to use unarmed strike damage, from the CRB grapple section:
Damage: You can inflict damage to your target equal to your unarmed strike, a natural attack, or an attack made with armor spikes or a light or one-handed weapon. This damage can be either lethal or nonlethal.