FlyHappy said most of what I wanted to say....
I left Air Wisconsin after just under 2 years in the right seat of the RJ for a pure 91 job as a co-captain on a 24 year old Citation II. I got to move back to the EXACT location my wife and I wanted to live in and my compensation was equal to if I had stayed at AWAC and upgraded. Most importantly to me, my QOL is outstanding...something even living in domicile at AWAC couldn't provide me.
Normally it is VERY difficult to make a jump from 121, especially a regional, to a corporate job. Why? One word-networking. The only reason I got my job was because I had strong recommendations from two friends (one current and one former pilot for them) to the owner. Its kinda hard to network for a corporate job by sitting in a crewroom in PHL, ATL or ORD, and its not as simple as walking into a Million Air somewhere and handing out resumes.
Ever heard the term "airline stink"? Corp operators often are biased against airline folks because their old airline habits die hard, and they lack the required customer service abilities (think concierge) to succeed in the job. Driving the airplane is easy....but most everything else (being your own dispatch/scheduling/mx control) is foreign. That bias isn't always fair, but its out there. Going from a regional to a 135 operator or a fractional for a year or two, as previously mentioned, is a great way to "wash" away the "stink".
90% of the time, the only way you are even considered for a F500 job (definitely a F100 job) is by having networked extensively AND having a strong resume. You may have the first part, but coming straight out of flight school odds are strong you'll substantially lack on the second part. A regional can serve a means to that end by quickly providing quality multi-turbine time, but you've got to develop and maintain the relationships you've made in 91/135 while working at a regional for it to be of any real benefit to you.
A corporate job does not automatically mean you'll be satisfied with your career. There are lots of crappy corporate jobs, many decent/good ones, but very few GREAT ones. I'm REALLY happy in my position and will only leave voluntarily for that great "brass ring" job...