Use, undress, unpack, unlock, unfold and unfasten are doing words. They begin with the letter u.
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Doing
The longest word starting with E is Electroencephalographically.
A four letter word starting with the letter a is able.
Okay, Here I am doing a project on this and I am able to help you. One word starting with B is bookkeeper. Another (this is not considered cheating) is bookkeeping. If you needed a word that did not start with B I will add in a word that could probably describe 50% of the world, sweettooth! I hope this helps and that it will inspire you to search for more words of this odd nature.
A seven letter word starting with E could be epitome.