The vast majority of the business community relies on poorly designed software. Though Twitter, Reddit, Facebook... are all impressive products, they have little "value" in the sense of building airplanes, treating medical patients, or running a country.
Apps in industry need to go beyond functional and user friendliness, they need to be user intuitive. Surely medical document management, social services, government run institutions, and even big nameless corporations need better software - how do we get through their (IT) gates?
In contrast to the B2C market for web 2.0 apps where consumers expect everything to be free, once you break into the corporate markets there are customers willing to pay big bucks for your product.
The primary problem is selling into this market. There are a lot of technicalities and the customers don't decide to buy after your first meeting. It requires a prolonged effort. If you get a programmer and a savvy salesman with experience in selling to large companies together I think there might be gold at the end of the rainbow though.