Any chance you were trying to get more than one flight at a time? I've seen KLM be very funny about married segments.

I ran into this issue with KLM where SFO-AMS available, AMS-BCN available, but SFO-AMS-BCN not available on the very same flights.

We could confirm one, or the other, but not both on the same record. You can possibly work around that by taking a stopover in AMS.

You can use either the general CO res folks, or the partner desk. The folks at the partner award desk are better at handling tough situations because they do it day in and day out. They're open M-F during extended business hours and are based in SLC and can be reached at 1-800-344-3333, one of the optoins is for KLM.