I don't know of any company that offers this type of service (even if it does exist I don't imagine it would be free) but, really, talking on the telephone is probably the incorrect medium when it comes to programming.
Obviously if you are just looking for lecture with no visual aids, code samples, etc then it is a fine medium but being that you want to ask coding questions (thus I assume you have XYZ bit of code you are having problems with) forums like this are great for that. Obviously you do not have the instant feedback that you would with, say, a live chat but you are relying on the person you are talking to to have "all of the answers". On forums you have many different sets of eyes looking at a question and while one user may give you x answer, another user may come along and further expand on that answer thus giving you a more "complete" answer on your question.
Anyway, sorry for my rant there, but if you are looking for a live chat I would probably poke around IRC and see what you could come up with. The last time I was on the Yahoo chat rooms (years ago) the programming rooms were almost always occupied with trolls of varying degrees and it was rare that you would find someone who A) you could actually talk to on a reasonable level and B) someone that was able to actually answer your question.
hth.
-Doug
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Read this if you want to know how to get a correct reply for your question:
http://www.catb.org/~esr/faqs/smart-questions.html
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.: Wrox Technical Editor / Author :.
Wrox Books 24 x 7
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