A general strategy for the directed and stereocontrolled assembly of carbon鈥揷arbon linked heterodimeric hexahydropyrroloindoles is described. The stepwise union of complex amines in the form of mixed diazenes followed by photoexpulsion of dinitrogen in a solvent cage provides completely guided assembly at challenging Csp3鈥揅sp3 and Csp3鈥揅sp2 connections.