Hmm, I think you need to give us a bit more info - your proposed circuit, 
supply voltage, etc. The mosfet and inductor won't complain much at 100C, 
but your LEDs might start to! And any electrolytic caps wont be winning any 
Long Service awards at those temperatures... Is the Mosfet running at this 
temp barbecue it is dissipating power, or is just in a hot place to begin 
with?

Make sure you are indeed switching the Mosfet cleanly - check the Vgs 
curves in the spec sheet. Remember that at high frequencies, the gate of a 
mosfet just looks like a capacitor - you really have to DRIVE current in to 
it - are you relying solely on the output of the SMPS IC?

Re series and parallel LED combinations - general rule of thumb is to 
arrange your LED load closest to the supply voltage, so that your SMPS is 
not having to step up or down too far from the supply rail, in either 
direction. You will see losses if you go for a very low voltage but high 
current output, or vice-versa

My two milliamps' worth -

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