Abstract: An (R/S)-titanium (IV) BINOLate-catalyzed highly enantioselective intramolecular Heck/aza-Diels–Alder cycloaddition (IHADA) cascade was developed to prepare tetrahydropyridoindoles (tHPs) and octahydropyrazinopyridoindoles (oHPPs) from in situ generated (R/S)-BINOL α-phosphoryl-ACHTUNGTRENNUNGoxy carbamate (αPPC2) in one pot. Chiral cooperativity between (R/S)-αPPC2 and (R/S)-titanium (IV)