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The only way you can add entries to the calibre toolbar is by writing a plugin. If the Open With plugin does not do the trick for you, then you will have to write your own.
Although I dont see what the extra steps are with the builtin open with functionality. In either case you need to make one click and then choose one entry from a popup menu. And you can even completely avoid all that, by simply assigning a keyboard shortcut to Open epub with Sigil in Preferences->Keyboard
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