Unprecedented Intramolecular [4 + 2]-Cycloaddition between a 1,3-Diene and a Diazo Ester

Journal of the American Chemical Society
Huang QiuMichael P Doyle

Abstract

Diazo compounds that are well-known to undergo [3 + 2]-cycloaddition provide the first examples of the previously unknown [4 + 2]-cycloaddition with dienes that occur thermally under mild conditions and in high yields. Reactions are initiated from reactants prepared from propargyl aryldiazoacetates that undergo gold(I)-catalyzed rearrangement to activated 1,3-dienyl aryldiazoacetates. These reactions proceed to mixtures of both [4 + 2]-cycloaddition and the 1,3-dienyl aryldiazoacetate after long reaction times. At short reaction times, however, both E- and Z-1,3-dienyl aryldiazoacetates are formed and, after isolation, thermal reactions with the E-isomers form the products from [4 + 2]-cycloaddition with ΔH(‡)298 = 15.6 kcal/mol and ΔS(‡)298 = -27.3 cal/(mol·°C). The Z-isomer is inert to [4 + 2]-cycloaddition under these conditions. The Hammett relationships from aryl-substituted diazo esters (ρ = +0.89) and aryl-substituted dienes (ρ = -1.65) are consistent with the dipolar nature of this transformation.

References

Feb 7, 2004·Chemical Communications : Chem Comm·Nan Jiang, Chao-Jun Li
Jul 14, 2005·Chemical Reviews·Shengming Ma
Apr 22, 2009·Journal of the American Chemical Society·Pablo MauleónF Dean Toste
May 17, 2002·Angewandte Chemie·K C NicolaouGeorgios Vassilikogiannakis
Dec 8, 2009·Organic Letters·Ana Z González, F Dean Toste
Dec 18, 2010·Chemical Communications : Chem Comm·Teng-Yue JianSong Ye
Jun 8, 2011·Beilstein Journal of Organic Chemistry·Lei ZhouJianbo Wang
Apr 12, 2012·Journal of the American Chemical Society·Roohollah Kazem ShiroodiVladimir Gevorgyan
Jul 10, 2012·Journal of the American Chemical Society·John F Briones, Huw M L Davies
Nov 23, 2012·Chemical Society Reviews·Géraldine MassonGuillaume Dagousset
Feb 28, 2013·Chemical Society Reviews·Roohollah Kazem Shiroodi, Vladimir Gevorgyan
Jun 19, 2013·Chemical Reviews·Annette D Allen, Thomas T Tidwell
Jun 19, 2013·Journal of the American Academy of Dermatology·Alastair Carruthers, Jean Carruthers
Nov 10, 2013·Beilstein Journal of Organic Chemistry·Fernando López, José L Mascareñas
Nov 16, 2013·Accounts of Chemical Research·Yi-Ming WangF Dean Toste
Feb 26, 2014·Accounts of Chemical Research·Louis Fensterbank, Max Malacria

❮ Previous
Next ❯

Citations

Sep 9, 2016·The Journal of Organic Chemistry·Kostiantyn O MarichevMichael P Doyle
Jan 18, 2017·Journal of the American Chemical Society·Abing DuanK N Houk
Jul 21, 2017·Chemical Society Reviews·Qing-Qing ChengMichael P Doyle
Mar 30, 2017·Chemical Society Reviews·Ying Xia, Jianbo Wang

❮ 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.