Unless I have any breakfast, I will be hungry at work.
Can I change this sentence, using "without"?
E.g- Without having any breakfast, I will be hungry at work.
Is it natural for using "without" to rephrase the "unless" structure?
You could say:
Without breakfast, I will be hungry at work.
If using 'unless' like in your first sentence, you don't need the 'any' (you could also replace the 'any' with 'some'):
Unless I have (some) breakfast, I will be hungry at work.
But I would say that the most natural way to phrase this sentence would be:
If I don't have breakfast, I will be hungry at work.