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Union is also known for her performances in the romantic comedy films The Brothers (2001), Deliver Us from Eva (2003), Daddy's Little Girls (2007), Think Like a Man (2012) and Think Like a Man Too (2014).She also had starring roles in CBS medical drama series City of Angels (2000) and films Bad Boys II (2003), Cradle 2 the Grave (2003), the critically acclaimed Neo Ned (2005), Cadillac Records (2008), and Top Five (2014).
She appeared in the ABC series Flash Forward alongside John Cho and Joseph Fiennes as Zoey Andata, a role for which she was nominated for an NAACP Image Award for Outstanding Supporting Actress in a Drama Series in 2010.She also appeared in Sister, Sister as Vanessa, in Smart Guy as Denise, and in five episodes of 7th Heaven as Keesha Hamilton. In the same year, she performed the role of Isis in the cheerleading movie Bring It On, opposite Kirsten Dunst. It led to Union being cast in the CBS television drama City of Angels as Dr. Union was featured in The Brothers and was seen as having a "beguiling sincerity, even when she's fudging the truth." Union was cast in her first leading role in the 2003 film Deliver Us from Eva with LL Cool J.This was her second time working with the rapper since making a cameo in his video "Paradise" in 2002.Union felt that she had been "blessed" with her role in the film, feeling it elevated her career.