igrockspock has a couple of Pepper-centric (Pepper/Tony) pieces: The Right Thing in the Wrong Way (http://archiveofourown.org/works/800847) and The Pregnancy Scare (http://archiveofourown.org/works/808480). They've also done a fair bit of Natasha- and Maria Hill-centric stuff, but rather than link a dozen more fics, I'd say if these Pepper ones are up your alley check out those too.

Hariboo's Pendulum: Beginning (http://archiveofourown.org/works/496214/chapters/868872) is very Jane-centric, and there'a also the Sif-centric The Salt Skin (http://archiveofourown.org/works/260182/chapters/406942), both of which are great.