Treatment of o-nitrostyrenes with aqueous TiCl3 solution at room temperature afforded indoles via a formal reductive C(sp2)-H amination process. A range of functions such as halides (Cl, Br), carbonyl (ester, carbamate), cyano, hydroxyl and amino groups were tolerated. From β, β-disubstituted o-nitrostyrenes, 2,3-disubstituted indoles were formed via a domino reduction/cyclization/migration process. Mild conditions, simple experimental procedure, ready accessibility of the starting materials and good to excellent yields characterized the present transformation. The methodology was used as a key step in a concise synthesis of rizatriptan and a formal total synthesis of aspidospermidine.