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Suppose I have a paladin in a fight with a tiger. We roll initiative, and the paladin is going to go last. In the first round, the tiger charges and deals 54 damage to my paladin, and takes them down.

I haven't had my turn yet. Can I use Hero's Defiance to use lay on hands, now that my paladin's going unconscious?

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No.

A paladin which has not yet acted in combat is flat-footed, barring some specific trick to counter that.

As SRD tells us (emphasis mine)

Immediate Actions

Much like a swift action, an immediate action consumes a very small amount of time but represents a larger expenditure of effort and energy than a free action. However, unlike a swift action, an immediate action can be performed at any time—even if it's not your turn. Casting feather fall is an immediate action, since the spell can be cast at any time.

Using an immediate action on your turn is the same as using a swift action and counts as your swift action for that turn. You cannot use another immediate action or a swift action until after your next turn if you have used an immediate action when it is not currently your turn (effectively, using an immediate action before your turn is equivalent to using your swift action for the coming turn). You also cannot use an immediate action if you are flat-footed.

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  • \$\begingroup\$ This answer is correct assuming there was either no surprise round or that the paladin was unable to act during the surprise round. Since most people call the round after the surprise round "the first round", there's just the tiniest bit of ambiguity in the question. I spend too much time on Puzzling.SE :P +1 \$\endgroup\$ – gatherer818 Nov 25 '14 at 13:06
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    \$\begingroup\$ @gatherer818 since both tiger and paladin are rolling initiative, they both have not yet the possibility to act and they both gained such a possibility simultaneously (in the same round). Therefore, the ambiguity there does not have any meaningful effect. \$\endgroup\$ – Jeor Mattan Nov 25 '14 at 13:12
  • \$\begingroup\$ I'm not sure how I didn't catch that. Excellent point. \$\endgroup\$ – gatherer818 Nov 25 '14 at 13:15

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