Photoinduced Cycloaddition and Ene Reactions of 2,7-Cyclooctadienone: Experimental and Computational Studies of a Cyclopentyl Oxyallyl Intermediate

doi:10.1021/JA984128G

Paper

Photoinduced Cycloaddition and Ene Reactions of 2,7-Cyclooctadienone: Experimental and Computational Studies of a Cyclopentyl Oxyallyl Intermediate

Published Feb 27, 1999 · A. Matlin, P. M. Lahti, D. Appella

Journal of the American Chemical Society

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Abstract

The photochemical reactions of cyclooctadienone 6 have been studied as a mode of entry to a cyclopentyl−oxyallyl system. Irradiation of cis,cis-2,7-cyclooctadienone 6 results in isomerization to cis,trans-2,7-cyclooctadienone 24. The strained dienone 24 is stable at −70 °C, but undergoes conrotatory cyclization at temperatures above −30 °C to the cis-bicyclo[3.3.0]oxyallyl system 25. The density functional theory (DFT) structural optimizations for 6, 24, and 25 at the 6-31G* B3LYP level yielded energies, selected geometric parameters, and charge/spin population data. The oxyallyl intermediate reacts with vinyl ethers in a stepwise fashion to give bridged and fused tricyclic products with defined stereochemistry at the ring junctures. Simple alkenes react with 25 in a concerted ene reaction to give bicyclic products. An explanation is offered to harmonize the traditional zwitterionic view of oxyallyl systems with the current computational assessment of oxyallyls as diradical species.

Study Snapshot

Photoinduced cyclloaddition of 2,7-cyclooctadienone leads to cis-bicyclo[3.3.0]oxyallyl system, which can be reacted with vinyl ethers to produce bridged and fused tricyclic products, and with simple alkenes to produce

PopulationOlder adults (50-71 years)

Sample size24

MethodsObservational

OutcomesBody Mass Index projections

ResultsSocial networks mitigate obesity in older groups.

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Paper

Photoinduced Cycloaddition and Ene Reactions of 2,7-Cyclooctadienone: Experimental and Computational Studies of a Cyclopentyl Oxyallyl Intermediate

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References

Citations

A Nazarov‐Ene Tandem Reaction for the Stereoselective Construction of Spiro Compounds

The tandem Nazarov/ene cyclization tandem reaction effectively creates stereoselective bicyclic spiro compounds, providing a strategic intermediate for total syntheses.

Air-stable Oxyallyl Patterns and a Switchable N-Heterocyclic Carbene.

Mesoionic pyrimidine derivatives with air-stable 1,3-bis(dimethylamino)oxyallyl patterns enable reversible switching of the electronic properties of an N-heterocyclic carbene moiety.

A computational study of the interplay of steric and electronic effects in the stabilization of 1,3-(diamino)oxyallyls

Amino-substituted 1,3-(diamino)oxyallyls can be stabilized enough for solution NMR spectroscopy, with the role of substituents playing a crucial role in stabilization.

The quest for observation and isolation of oxyallyl derivatives

Oxyallyl derivatives have become attractive synthetic targets with potential applications in advanced materials science, after 40 years of research.

Nazarov reactions intercepted by (4 + 3) cycloadditions with oxygen-substituted dienes.

Regioselective (4 + 3) cycloadditions with oxygen-substituted dienes can effectively intercept the oxyallyl cation intermediate in Nazarov reactions, with some stereoselectivity due to steric interactions.

The pivotal role of oxyallyl diradicals in photo-Favorskii rearrangements: transient spectroscopic and computational studies.

Oxallyl diradicals play a crucial role in photo-Favorskii rearrangements and their stability can be improved by stabilizing open-shell singlet diradicals.

Photocycloadditions of tetrachloro-1,4-benzoquinone (chloranil) onto cyclobutene and cyclopropene. Expected and unexpected products.

Photocycloadditions of chloranil to cyclobutene and cyclopropene yield expected products and unexpected products, including a tetracyclic acetal with a cyclopentanone and dihydropyran subunit.