Your code looks like it will form the correct API call URL to make.
Things to check:
Does the back-end service support version 1.4 of the LP component's APIs? I suppose that it does, because you say you made a whoami call successfully.
What kind of error are you getting from the call? If you're getting a 404, then the service can't find a record that matches your user name, or it can't bind a handler to the route you provide at all (for example, if you use a version number the service doesn't support, or you have a spelling mistake in the route, or you forget a trailing slash when it should be there)--in this case, those latter cases seem unlikely, so if you're getting a 404, I suspect it's because the call can't find the user record to match your provided name.
Do you know the D2L ID of the user you're trying to bring back? If so, try fetching just that resource with GET /d2l/api/lp/1.4/users/(userId) and verify that the UserName property contains the user name that you expect to be searching upon.
Are you sure your user context is able to use this route to look at user records? Unlike whoami, this call is essentially in the administrative space (because it doesn't include an org unit ID in the route, it operates at the organization-wide level), so unless your user context has administrative permissions, it's unlikely you can use this call at all (or your use of it will be tightly restricted).
Keep in mind also that the UserName is a bit of personally identifying information and is subject to privacy controls: the user context making the API call must have permissions to see the user name property for users. (I believe that, if this is the problem, you'll get a 403 response when trying to use this call -- just as you would if you don't have permissions to use the API call to see user records at all.)