A couple college friends are on the corporate track right now. One went to airline training, didn't like it, and came back home. He then came back home, found a job flight instructing and flying some charter work. The charter work lead to a job flying in a bank's corporate flight department, and he was just recently typed on their jet. Another couple guys found different flight instruction type jobs that in addition would have them fly right seat on the flight schools king air. The company does charter work in the king air, and has a couple of citations as well for charters and occasional life flight type work. Idea is to work your way from flight instructor, to right seat of the prop, left seat of the prop (get that turbine pic), then right seat on the jet, then PIC on the jet.
Finding these jobs is often the problem, sometimes you're competing with tons of guys, but often not. The companies will often be able to fill the jobs without even putting an ad in the paper, just from word of mouth of "my buddy flies, i bet he'd be interested." and so on. Right place right time seems to really fit.
Some corporate jobs also require you to be married to your cell phone. Yes, they can provide you with good pay, great locations, and the opportunity to bring your golf clubs along and play 18 while your management is in a business meeting. But, you've gotta be willing to live the "playboy" lifestyle for some time, expecting to make plans with your friends/family can be very difficult, if they can call you up the night before, or even day of and expect you to show up. A different friend of mine was doing that for quite some time. Said he hadn't stayed in a hotel in a month or so. Spends most of his time doing trips out and back. But, has no scheduled days off a month. I myself couldn't live with only know i had a day off the day after it occurred.
There have been a lot of regional and probably even some major guys going over to the fractionals. In a nutshell, most pay better than regionals, some much much better. The top tier one right now starts you off at a regional Captain wage in the mid to upper 60's. You'd expect a 7 day on and 7 day off schedule, and a much nicer quality of life. Down this avenue though, you will be dealing with tons of direct competition from other airline pilots, as many would LOVE to land this job.