Our district has a new superintendent. I was just about to hit "Send" on an email to the new supt., but thought I should ask here first about the appropriateness of going straight to the top.
Within the walls of our school, I am careful to work with teachers first, and then follow-up with the principal... I'm quite mindful of stepping on toes here.
But at the district level, unless you were complaining about some issue in the school (which should go to the principal first), I can't think of any reason to start elsewhere. (However, it wouldn't hurt to let the principal know in advance -- not so much for permission, but as a courtesy -- just so he's not surprised down the road.)
"... in this case, should I proceed boldly?"
Given that I am an unabashed Star Trek fan, I'm sure you can guess my answer to that question!