(R/S)-BINOL-α-Phosphoryloxy Enecarbamate-Mediated and (R/S)-Titanium(IV) BINOLates-Catalyzed Enantioselective Intramolecular Heck/Aza-Diels-Alder Cycloaddition (IHADA): An Expedient Methodology

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 -phosphoryloxy carbamate (PPC2) in one pot. Chiral cooperativity between (R/S)-PPC2 and (R/S)-titanium(IV) BINOLate was observed and successfully utilized for the construction of various tHPs (7 examples) and oHPPs (17 examples).