Here in California, at least, yes. The local ATMs give 100s and 50s, and only twenties if you are specifically drawing 20 or 40 bucks.
Legal tender for all debts.
The point stands that, in my experience, $100 bills are an outlier in most of the US and will, at a minimum, invite additional scrutiny or simply be refused in many situations.
That’s not what that means
So yes, they could refuse the $100 and then sue me, at which point they'd have to take it. So you'd get a big clap for technically "winning" this argument but in possibly the dumbest way possible.
In practice, the reason why 'legal tender for all debts' is relevant is because it pretty much forces to take my $100 or go through an expensive process to just end up with the same result.