%0 Journal Article %A Hanessian, Stephen %A Tremblay, Martin %D 2004 %T Tandem Functionalization of Nonactivated Alkenes and Alkynes in Intramolecular N-Acyloxyiminium Ion Carbocyclization. Synthesis of 6-Substituted Hydroindole 2-Carboxylic Acids %U https://acs.figshare.com/articles/journal_contribution/Tandem_Functionalization_of_Nonactivated_Alkenes_and_Alkynes_in_Intramolecular_i_N_i_Acyloxyiminium_Ion_Carbocyclization_Synthesis_of_6_Substituted_Hydroindole_2_Carboxylic_Acids/3312910 %R 10.1021/ol040053b.s002 %2 https://acs.figshare.com/ndownloader/files/5151640 %K esters %K tandem Functionalization %K octahydroindole %K butenyl %K Intramolecular N %K halo %K Synthesi %K methyl %K carboxylic %K Alkyne %K Heck %K arylated azabicyclics %K substrate %K sp 3 %K carbocyclization %K cyclic vinyl bromides %K acid %K Suzuki %K tethers %K chemical diversification %K scaffold %K access %K Substituted %K method %K stereodefined %K enantiopure sp 2 %K Hydroindole %K hexahydroindole %K butynyl %K Carboxylic %K Nonactivated Alkenes %K Acyloxyiminium Ion Carbocyclization %K Friedel %K Acid %K Lewis %K Boc acyliminium ions %K Stille couplings %X Five-membered N-Boc acyliminium ions derived from l-pyroglutamic acid harboring 4-butenyl and 4-butynyl tethers undergo Lewis acid-mediated halo and tandem Friedel−Crafts carbocyclization within minutes at −78 °C to give stereodefined 6-substituted octahydroindole and hexahydroindole 2-carboxylic acid methyl esters, respectively. The cyclic vinyl bromides are excellent substrates for Pd-catalyzed Suzuki−Miyaura, Heck, and Stille couplings. The method also provides access to enantiopure sp2- and sp3-arylated azabicyclics that are novel and versatile scaffolds for chemical diversification. %I ACS Publications