I think there are two issues with 215.2 -- you can size feeders that comply with all the restrictions of 310.15(B)(6), and you can install a feeder of whatever ampacity you want and not have to exceed the size of the service entrance conductors. You're doing the second and not the first. Note that if the calculated load of that feeder was truely 100A, then your service would most likely have to be upgraded because of all the other loads in the main panel. This could also be dangerous if you had multiple service disconnecting means instead of a single 100A main, as it would be easy to exceed the calculated load.
If you had a 125A service and wanted to run a 100A feeder with #2 AL, then you'd be into the debatable section of 310.15(B)(6) and most here seem to take the interpretation that this would not be allowed. But a 100A feeder on a 100A service using #2 AL should be OK assuming the service entrance conductors were #2 AL.