Spontaneous inequilibrium in a gas in an isolated system?
The short answer to the question "Can an isolated system(of several phases) in equilibrium by itself move out of equilibrium?" is NO.  Once the system is in equilibrium it will remain there.

If it is possible, as is asked in the second part of the question, to have some reaction be triggered at a higher temperature reached by fluctuation, then as has been commented, the answer is that the system was never in equilibrium.

We should never forget that there is no "absolute" starting temperature for a reaction.  If the reaction is physically possible, it will take place, but the rate of that reaction can be horribly slow.