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The ’ et al codes are not Unicode, they are HTML entities, and work whatever the real encoding of the file is.
You can write explicitly the needed character, but then it has to be in the correct declared encoding (and in ePUB, it must utf-8 or utf-16). If you mix encodings bad things happen.
A trick: when I need to differentiate between single quotes and apostrophes, I use ‘ ’ for the quotes and & #8217; (without space) for the apostrophe. The character is exactly the same, but that allows for better search and replace in the future. I don't know if Sigil would keep this, though.
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