It's a great method to get inspiration for potential problems in the B2B space. The challenge however, after you've come up with a solution is the sales. Enterprise sales are notoriously difficult especially due to "big business" culture that creates inefficiencies to solve in the first place.
"Start by writing software for smaller companies, because it's easier to sell to them. It's worth so much to sell stuff to big companies that the people selling them the crap they currently use spend a lot of time and money to do it. And while you can outhack Oracle with one frontal lobe tied behind your back, you can't outsell an Oracle salesman. So if you want to win through better technology, aim at smaller customers."
PG has this to say in his essay (http://paulgraham.com/start.html) :
"Start by writing software for smaller companies, because it's easier to sell to them. It's worth so much to sell stuff to big companies that the people selling them the crap they currently use spend a lot of time and money to do it. And while you can outhack Oracle with one frontal lobe tied behind your back, you can't outsell an Oracle salesman. So if you want to win through better technology, aim at smaller customers."