In one case, an employee was going to work for a startup developing a new (completely novel) product in the same industry as former company. There was a non-compete clause in the employment contract. It was cheaper to wait a year before joining the startup than to litigate. I know both companies, and the claim of competition was tangential at best.

In another case, an employee hadn't signed the current employment agreement which was far more overreaching than the terms of employment they originally agreed to (but which were needed for the organization to pursue its new -- somewhat sleazy -- business model).

The organization fabricated criminal allegations and told the employee they would press charges if the employee didn't sign away their rights. That's criminal extortion, but if such threats are verbal, it's not something you can really prove. Best case outcome for employee was a (very public) mud throwing match against an organization with an extensive PR/press department. A lawyer took that one pro bono, but I think that cost that employee 3-6 months of their life, and in the end, they gave up on their next startup too (which was, again, in the same industry as their former employer, and difficult to do with new terms).

Both were big organizations (ones you would have heard of, and one of which is held in extremely high esteem as an 'ethical' organization). Both settlements involved signing away rights to talk about those settlements.