Tandem Functionalization of
Nonactivated Alkenes and Alkynes in
Intramolecular N-Acyloxyiminium Ion
Carbocyclization. Synthesis of
6-Substituted Hydroindole 2-Carboxylic
Acids

Hanessian, Stephen; Tremblay, Martin

doi:10.1021/ol040053b.s002

Cite Download Share Embed

Tandem Functionalization of Nonactivated Alkenes and Alkynes in Intramolecular N-Acyloxyiminium Ion Carbocyclization. Synthesis of 6-Substituted Hydroindole 2-Carboxylic Acids

2004-12-09T00:00:00Z (GMT) by Stephen Hanessian Martin Tremblay

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.

Keyword(s)

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

License

CC BY-NC 4.0

Export

RefWorks

BibTeX

Endnote

DataCite

NLM

Tandem Functionalization of Nonactivated Alkenes and Alkynes in Intramolecular N-Acyloxyiminium Ion Carbocyclization. Synthesis of 6-Substituted Hydroindole 2-Carboxylic Acids

Categories

Keyword(s)

License

Export