That is strange. Are you sure your smart quotes are truly unicode smart quotes, and not microsoft cp smart quotes or latin-1 smart quotes? And what dictionary are you testing this with? Is it the en_US dictionary? Or one of your on wordlist dictionaries.
The Hunspell en_US dictionary we use always converts words with all smart quotes to dumb ones, before attempting to check the word, as this is how the words in the en_US dictionary are stored. So if you add your owns words to a wordlist, you should be doing the same.
Also what version of Sigil are you using?
And are the epub's xhtml files properly utf-8 encoded? (if you input from Windows text files this is rarely the case as Windows is stuck with legacy codepage text encoding instead of straight utf-8).
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