Enantiodivergent [4+2]-Cycloadditions of Dienolates by Polyfunctional Lewis-Acid / Zwitterion Catalysis

Angewandte Chemie
Vukoslava Miskov-PajicRené Peters

Abstract

Diels-Alder reactions are established as one of the most effective ways to prepare stereochemically complex 6-membered rings. Different catalysis concepts have been reported including dienophile activation by Lewis acids or H-bond donors and diene activation by bases. Here we report a new concept, in which an acidic prodiene is acidified by a Lewis acid to facilitate deprotonation by an imidazolium-aryloxide entity within a polyfunctional catalyst. A metal dienolate is thus formed, while imidazolium-ArOH moieties probably form hydrogen bonds with the dienophile. The catalyst type which is readily prepared in few steps with high overall yields, was applied to 3-hydroxy-2-pyrone and -pyridone as well as cyclopentenone prodienes. Maleimide, maleic anhydride, and nitroolefin dienophiles were employed. Kinetic, spectroscopic and control experiments support a cooperative mode of action. Unprecedented TONs up to 3680 were achieved still attaining high enantioselectivity.

References

Jun 13, 2002·Chemical Reviews·Masakatsu Shibasaki, Naoki Yoshikawa
Jul 18, 2002·Chemical Communications : Chem Comm·Donato MontiGiovanna Mancini
Mar 10, 2005·Bioorganic & Medicinal Chemistry·Takeshi YamashitaYoshinobu Ishikawa
Mar 1, 2006·Chemical Society Reviews·Masakatsu Shibasaki, Shigeki Matsunaga
Mar 31, 2007·Journal of the American Chemical Society·Shinya HandaMasakatsu Shibasaki
May 2, 2007·Journal of the American Chemical Society·Yi WangLi Deng
Jan 29, 2008·Organic Letters·Nsiama Tienabe KipassaTetsuo Iwagawa
Sep 20, 2008·Organic & Biomolecular Chemistry·Juan Shen, Choon-Hong Tan
Oct 24, 2008·Chemical Reviews·Sébastien Reymond, Janine Cossy
May 6, 2009·Journal of the American Chemical Society·Julian Ying-Teck Soh, Choon-Hong Tan
May 14, 2009·Accounts of Chemical Research·Masakatsu ShibasakiNaoya Kumagai
Dec 17, 2011·Chemical Science·Keith J BartelsonLi Deng
Feb 14, 2012·Journal of the American Chemical Society·Ryan D BaxterDonna G Blackmond
Jun 22, 2012·Accounts of Chemical Research·Jun-Long LiYing-Chun Chen
Jul 31, 2012·Chemical Society Reviews·Jongwoo Park, Sukwon Hong
Jan 27, 2015·The Journal of Organic Chemistry·Jun IshiharaSusumi Hatakeyama
Aug 19, 2015·Journal of the American Chemical Society·Donna G Blackmond
Nov 3, 2016·Chemical Society Reviews·Vanesa Marcos, José Alemán
Nov 25, 2016·Chemical Society Reviews·Lydia KlierKarl Anker Jørgensen
Jan 6, 2017·Chemical Communications : Chem Comm·Florian BroghammerRené Peters
Sep 9, 2017·Angewandte Chemie·Le LiuStefan Matile
Oct 3, 2017·Accounts of Chemical Research·Xiaohua LiuXiaoming Feng
Feb 13, 2019·Chemical Science·Christian D-T Nielsen, Jordi Burés

❮ Previous
Next ❯

Citations

Jun 25, 2021·Chemical Science·Xinyi Ye, Choon-Hong Tan

❮ Previous
Next ❯

Methods Mentioned

BETA
gel filtration

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.