I doubt that the lack of rounded corners is going to give anyone issues with the Metro/Modern/whatever style. The list of things with entirely rectangular buttons includes Windows prior to XP, most other older non-Mac window managers and OSes, and a vast number of real-world products like stereos and TVs. The very top thing on that link is an update basically saying it's an unresolved question: "My rounded rectangles cognitive argument is getting a good thrashing — which is a good thing. I'm as keen as anyone to find out if the theory holds water, and if you can direct me to better research, I'd love to read it. Please share!" I don't buy it, personally. Maybe the reason signs in public places have rounded corners, like the famous No Parking sign Jobs showed, is just to avoid having sharp corners for safety? Then there's stuff like the utterly-minimal rounding of Lion/Mountain Lion buttons: they'd fall pretty high on that cognitive cost scale he posits, especially compared to the Aqua ones they replaced.
The lack of hinting that one element is clickable/tappable while another is a bigger issue, though, than just rounded edges. As far as web use of this style goes, I think the arrows-in-circles (or something similar) used on the main button on this page, and on the Windows Azure site mentioned elsewhere in the comments here will be key.
WP7 is pretty good about having "buttons" be styled fairly distinctively from other elements (they're circular in the menu bar at the bottom of an app, and in other places like the "More Details" button when editing a calendar appointment they get a thick distinctive border.
When your style is minimal you need to be very careful and consistent with the meaning of what visual cues you do have, so how stuff like that will translate to the web—especially if someone just wants to make a site look "Metro" but isn't so familiar with the conventions)—is an open question.