I think I have proof that matlab does not respect the proxy server exclusions; if I set the proxy settings in matlab to point directly at my internal website - i.e. in matlab preferences, use this; http://10.65.15.180 then I can use webread as expected.
I guess I'd like to submit an enhancement request to the mathworks, that webread should respect the list of exclusions in the default windows proxy settings. Anyone know how I can do that ?