It's very likely, that we don't have discovered every non man-made element. For some elements there exist only very short-lived isotopes.
Plutonium...
is the heaviest primordial element by virtue of its most stable isotope, plutonium-244, whose half-life of about 80 million years is just long enough for the element to be found in trace quantities in nature
More about naturally occurring nuclides.
This paper mentions the detection of a curium ion in cosmic rays.
The process which forms curium can also form elements beyond curium, hence it's likely that there exist short-lived isotopes of elements in nature, which have not yet been detected. Research in this field is going on.
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