Tandem Functionalization of Nonactivated Alkenes and Alkynes in Intramolecular <i>N</i>-Acyloxyiminium Ion Carbocyclization. Synthesis of 6-Substituted Hydroindole 2-Carboxylic Acids Stephen Hanessian Martin Tremblay 10.1021/ol040053b.s002 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 Five-membered <i>N</i>-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 sp<sup>2</sup>- and sp<sup>3</sup>-arylated azabicyclics that are novel and versatile scaffolds for chemical diversification. 2004-12-09 00:00:00 esters tandem Functionalization octahydroindole butenyl Intramolecular N halo Synthesi methyl carboxylic Alkyne Heck arylated azabicyclics substrate sp 3 carbocyclization cyclic vinyl bromides acid Suzuki tethers chemical diversification scaffold access Substituted method stereodefined enantiopure sp 2 Hydroindole hexahydroindole butynyl Carboxylic Nonactivated Alkenes Acyloxyiminium Ion Carbocyclization Friedel Acid Lewis Boc acyliminium ions Stille couplings