Biomimetic 2-Imino-Nazarov Cyclizations via Eneallene Aziridination.

Journal of the American Chemical Society
Joshua R CorbinJennifer M Schomaker

Abstract

Amidoallyl cations are appealing three-carbon synthons for the preparation of complex amine-containing carbocycles; however, methods to generate and utilize these reactive species are limited and underexplored compared to those for oxallyl cations. Here we disclose a bioinspired strain-driven ring opening of bicyclic methyleneaziridines to 2-amidopentadienyl cation intermediates that readily engage in Nazarov cyclizations. Advantages of this strategy include ease of generation and improved reactivity compared to 3-pentadienyl cations, control over the ultimate position of the alkene, the potential for high dr between vicinal stereocenters, and the ability to further elaborate the products to fully substituted aminocyclopentanes. Experimental and computational studies support a dual role for the Rh2Ln complex as both a nitrene transfer catalyst and a Lewis acid promoter, insight that provides a framework for the future development of asymmetric 2-imino-Nazarov cyclizations.

References

Jun 5, 2002·The Plant Cell·John G TurnerAlessandra Devoto
Nov 28, 2002·Journal of the American Chemical Society·Michael Harmata, Dong Reyoul Lee
Sep 8, 2004·Chemistry : a European Journal·Olalla Nieto FazaAngel R de Lera
Jul 26, 2008·Journal of the American Chemical Society·Xiaotao Pu, Joseph M Ready
Dec 9, 2009·Journal of the American Chemical Society·Armin H Stoll, Simon B Blakey
Dec 25, 2009·Organic Letters·William F BowMarcus A Tius
Apr 7, 2010·Chemical Communications : Chem Comm·George C FeastJeremy Robertson
May 19, 2010·Organic & Biomolecular Chemistry·Jeremy RobertsonTimothy D W Claridge
Dec 16, 2010·Organic Letters·William T SpencerAlison J Frontier
Jan 31, 2012·The Journal of Organic Chemistry·John A MalonaAlison J Frontier
May 24, 2013·Organic Letters·Sara A BonderoffMartin Tremblay
Nov 8, 2013·Chemical Society Reviews·Marcus A Tius
Dec 7, 2013·The Journal of Organic Chemistry·Diana YuJason E Hein
Feb 6, 2014·Organic Letters·Hiroki TakahashiIkuya Shibata
Jun 19, 2014·Chemistry : a European Journal·Geoffroy DequirezPhilippe Dauban
Jun 20, 2014·Organic & Biomolecular Chemistry·Adán B González-PérezAngel R de Lera
Jun 21, 2014·Organic & Biomolecular Chemistry·Martin J Di Grandi
Jun 4, 2016·Chemistry : a European Journal·Jennifer CiesielskiPhilippe Dauban
May 13, 2017·The Journal of Organic Chemistry·Marcel Schlegel, Christoph Schneider
Sep 30, 2017·Organic & Biomolecular Chemistry·Maxim G VinogradovSergei G Zlotin

❮ Previous
Next ❯

Citations


❮ Previous
Next ❯

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.