The MSDN Library homepage has a newish “beta” quick links section which is a great index for navigating in an easier way than the somewhat dense tree nav:
MSDN Library
Welcome to the MSDN Library, an essential source of information for developers using Microsoft® tools, products, technologies and services. The MSDN Library includes how-to and reference documentation, sample code, technical articles, and more. To find the content you need, browse the table of contents, use search, or use a Quick Link to jump to some of the most popular areas of the library. To get the latest MSDN headlines sent to you via e-mail. Sign up for the MSDN Flash Newsletter.
Quick Links
Beta
Quick Links provide an easy way to jump to the information you are most likely looking for. We’re just testing the idea out right now, so please take a few minutes and give us some feedback on Quick Links.