Good answers above. I'd say no, 90% of the time. It does depend on how far along you are.
From an engineering or product perspective, I highly doubt anyone from a large company would be useful. The teams are used to long roadmaps, command and control, and large scale technical problems. Not exactly what you're dealing with in a startup. It's not just that you need generalists; you need people who are customer focused, iterate insanely quickly, and are unafraid to cut certain corners at the right time. Not a lot of corporate folks are like that.
From the sales side, as Venkat said above, the BD benefits can be great. However, good sales people are rather pricey, another thing you likely cannot deal with in a startup. If there are senior folks, and you can get them for mostly equity, make sure they have the contact list you need to do really solid BD. Then it might work. They still have to get used to the (lack of) systems/support and looser culture of a startup.
In short, it's a rough transition. Seen it many, many times. Rarely pays off.