#Klar, Ja klar, Na klar, Natürlich
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I mean
the first three are usually a sentence of their own
so if i say something you could answer "Na klar, so denke ich auch" or something like that; whereas Natürlich is an adverb (like selbstverständlich), so it can't make a sentence of its own
i would say "Natürlich ist es so/ es gibt doch natürlich eine Ausnahme...."
you wouldn't say "Natürlich." an that's it.
and
that's one thing off the top of my head