I dont think thats possible
What are your source files for generating epubs
normally calibre just checks H1 and H2 tags but most books I acquire use H3 for chapter heading so I use this for chapter detection
Quote:
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//*[((name()='h1' or name()='h2' or name()='h3') and re:test(., 'chapter|book|section|part\s+', 'i')) or @class = 'chapter']
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and this for page breaks before every chapter
Quote:
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//*[name()='h1' or name()='h2' or name()='h3']
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If chapters are still not detected I try to use notepad++ to add <h3> tags to the source files and use this in level 1 Toc as a last option never fails