Working at a startup is obviously very different from working in a corporate environment. You have to thrive on risk and be so passionate about new technologies that you can't help but learn all that stuff and chomp at the bit to use it.
I can't imagine working at Microsoft and NOT having learned HTTP, Razor, MVC 3, ASP.NET, CSS, HTML, JavaScript, jQuery, jQuery UI, Facebook Connect, Twitter API, SQL at this point. It is stunning how much a single person can get done these days thanks to all the cool technologies that have come along in the last few years. If that guy is truly dying to join a startup, why doesn't he have his own side project yet?
I think Calbucci is just trying to find people with true passion. I would definitely worry that this person moves on to a job with more $$$ if the startup isn't a huge success right out of the gate. After all, financial motivations are keeping him at his current job right now.
The founder probably took a 100% paycut to get it started. I don't think it's too much to ask for someone to take a financial risk to come onboard; especially when it's before launch, which means their cash flow is probably close to $0. Obviously, these kinds of decisions are not for everyone. But, when you're truly passionate, it's not really a choice at all.