Well, they other options are open. So it might make sense. :P
Up to you whether or not you're getting enough of a productivity gain to justify it.
- ASP.NET can scale, if you do it right. Aside from Microsoft.com/MSN, which don't really count, MySpace uses it (though they upgraded from ColdFusion, which wasn't much better) and Plenty of Fish, the web's largest dating site, uses it too: http://www.plentyoffish.com/about_team.aspx These are probably all larger than the most successful Rails sites.
- ASP.NET MVC isn't a horrible programming model. Forget the abomination that's normal ASP.NET with its funky events. If you've used another MVC framework like Rails or Cake, you'll feel right at home.
- Microsoft's startup program gives startups the early software for super cheap: http://microsoftstartupzone.com/
- It's all about getting v1 out and releasing early and often. If your team grew up on Microsoft, are you really going to make them all learn a new framework? If you do it right and prove out your idea, you can always rewrite later.
What would you recommend that career Microsoft developers use for their startups?
With what was Stack Overflow built?
:~)