No correlation, technically. I have a particularly bad case of PCOS, and my parents dragged me to every gender specialist to figure out if it was causing my GID. Eventually I ended up at Johns' Hopkins, where twelve doctors and authorities on GID sat on a panel, evaluated me, and told my parents that there is absolutely no correlation.
This is how I think of it: hormones aren't really a big issue until you hit puberty. PCOS doesn't become a problem until then, since it's not like you had excess testosterone before you hit puberty. But, did you identify with the male gender before puberty? I know I did, and thus it was before I had PCOS, so no correlation.
However, as someone pursuing a medical career, I've done some other research. PCOS isn't understood quite as well as it could be, but it has been speculated that it is hereditary. So let's say your mom has excess testosterone. She becomes pregnant with you (somehow despite having PCOS) and is unaware that she has PCOS, therefore you, a developing female fetus, receive a hefty dose of testosterone while in utero. This affects your brain development in such a way that it becomes more congruous with the brain of the male gender. Voila! A transman in the making.
So I guess what I'm trying to say is, yes, there could be a correlation, but it is irreversible. Luckily, it makes passing ten times easier before starting testosterone...as in, I have a beard in my before AND after pictures. Good stuff!