I did this at my job. I essentially took CLR Via C# (Jeffrey Richter's awesome book) and covered it chapter by chapter. Best thing is to skip the first couple chapters, as they go into detail about the CLR.
You can speed past much of the details, depending on your audience. With the groundwork laid, you can then hit the following subjects:
ASP.NET MVC (at this point I'd skip classic ASP.NET development)
Linq (covering lambdas, extension methods, and linq to XML)
WPF (bury winforms in the same hole with ASP.NET)
WCF (put .NET remoting in that same hole)
MVC doesn't have many books yet, and most of it is already outdated. But there are lots of tutorials and information on the internet available.
Linq isn't just about SQL, its about querying data. Its also a great place to introduce developers to lambdas and extension methods.
WPF... what can I say? Lots of good books out there. Probably the most important thing to teach is data binding. Model-View-ViewModel architectures and DependencyProperties make designing windows forms applications much simpler and more robust than the old winforms model with its hacky binding. Also XAML.