Application of<i>o</i>-Quinodimethanes in Organic Synthesis

Shifa, Zhu; Ruoshan, Zheng

doi:10.6023/cjoc201401006

Cited by 9 publications

(2 citation statements)

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“…First, when the reaction of enynal 1a and methyl phenyldiazoacetate 2a was conducted under optimized reaction conditions in the absence of alkene 3 , an interesting polycyclic compound 7a was isolated, which might come from the dimer of vinyl‐ o ‐QDM. [ 7 ] In addition to the product 7a , another cyclobutane 8a was also obtained in 70% yield. The structure and stereochemistry of 7a and derivation of 8a were further confirmed by the X‐ray diffraction analysis.…”

Section: Resultsmentioning

confidence: 99%

Rapid Access to Oxabicyclo[2.2.2]octane Skeleton through Cu(I)‐Catalyzed Generation and Trapping of Vinyl‐o‐quinodimethanes (Vinyl‐o‐QDMs)^†

Luo

Jiang

et al. 2020

Chin. J. Chem.

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A Cu(I)‐catalyzed three‐component reaction of terminal enynals/enynones, diazo compounds, and alkenes has been developed. With this method, a series of oxabicyclo[2.2.2]octanes were effectively synthesized in high yields under mild reaction conditions. This transformation is proposed to proceed through trapping of the cyclic vinyl‐o‐quinodimethanes (vinyl‐o‐QDMs) species, which were generated from terminal enynals/enynones and diazo compounds by alkenes.

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Section: Resultsmentioning

confidence: 99%

Rapid Access to Oxabicyclo[2.2.2]octane Skeleton through Cu(I)‐Catalyzed Generation and Trapping of Vinyl‐o‐quinodimethanes (Vinyl‐o‐QDMs)^†

Luo

Jiang

et al. 2020

Chin. J. Chem.

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“…We and Hammond and co-workers have found another pathway b, in which a highly active intermediate o-quinodimethane LXII (o-QDM) was generated via d-metal elimination. 54,59,60 The transient short-lived o-QDM species can undergo a second Diels-Alder reaction with alkenes or alkynes to furnish the fan-like products 111, otherwise there is a 1,5-H shift to afford 1,2-DHN in the absence of dienophiles.…”

Section: Reactions Via Pyrylium Intermediatesmentioning

confidence: 99%

Transition-Metal-Catalyzed Intramolecular Nucleophilic Addition of Carbonyl Groups to Alkynes

Chen

Zhu

2018

Chem

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Compounds consisting of a carbonyl group and an alkyne group, especially enynals and enynones, are versatile and powerful building blocks for generating structurally diverse polycyclic compounds. In the past decades, the transitionmetal-catalyzed nucleophilic addition of a carbonyl group to an alkyne has attracted great interest for the high reactivity, good selectivity, excellent functional-group tolerance, and mild reaction conditions. Most importantly, versatile intermediates, such as pyrylium-ion, metal-carbene, 1,3-dipole, and metal-vinyl species, make it highly attractive for both the development of synthetic methodologies and applications in the synthesis of bioactive compounds or complex naturally occurring skeletons. This review focuses on the transition-metal-catalyzed nucleophilic addition of carbonyl groups to alkynes with an emphasis on the scope and limitations, the mechanisms, and applications in organic synthesis.

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Zinc‐Catalyzed Tandem Diels–Alder Reactions of Enynals with Alkenes: Generation and Trapping of Cyclic o‐Quinodimethanes (o‐QDMs)

et al. 2016

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A systematic investigation of ZnCl2‐catalyzed reactions of enynals with alkenes has been undertaken. Structurally unique propeller‐like products could be obtained under mild conditions. Cyclic o‐quinodimethanes (o‐QDMs) are generated through [4+2] cycloaddition between enynals and alkenes. Both electron‐poor and electron‐rich dienophiles could be used to trap the active intermediate through [4+2] cycloaddition. But [1,5]‐H shift products could also be observed when electron‐rich alkenes were used as dienophile. DFT calculations were performed to understand the reaction mechanism. A competition between the [4+2] cycloaddition and [1,5]‐H shift was proposed for the transformation of cyclic o‐QDMs. The selectivity could be affected by the properties of the substrates.magnified image

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Application ofo-Quinodimethanes in Organic Synthesis

Abstract: o-Quinodimethane (o-QDM) is a highly active transient species. In this paper, the structures, properties, different generation ways, and application of this unique species are reviewed respectively in this paper.

Cited by 9 publications

References 35 publications

Rapid Access to Oxabicyclo[2.2.2]octane Skeleton through Cu(I)‐Catalyzed Generation and Trapping of Vinyl‐o‐quinodimethanes (Vinyl‐o‐QDMs)^†

Rapid Access to Oxabicyclo[2.2.2]octane Skeleton through Cu(I)‐Catalyzed Generation and Trapping of Vinyl‐o‐quinodimethanes (Vinyl‐o‐QDMs)^†

Transition-Metal-Catalyzed Intramolecular Nucleophilic Addition of Carbonyl Groups to Alkynes

Zinc‐Catalyzed Tandem Diels–Alder Reactions of Enynals with Alkenes: Generation and Trapping of Cyclic o‐Quinodimethanes (o‐QDMs)

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Application ofo-Quinodimethanes in Organic Synthesis

Abstract: o-Quinodimethane (o-QDM) is a highly active transient species. In this paper, the structures, properties, different generation ways, and application of this unique species are reviewed respectively in this paper.

Cited by 9 publications

References 35 publications

Rapid Access to Oxabicyclo[2.2.2]octane Skeleton through Cu(I)‐Catalyzed Generation and Trapping of Vinyl‐o‐quinodimethanes (Vinyl‐o‐QDMs)†

Rapid Access to Oxabicyclo[2.2.2]octane Skeleton through Cu(I)‐Catalyzed Generation and Trapping of Vinyl‐o‐quinodimethanes (Vinyl‐o‐QDMs)†

Transition-Metal-Catalyzed Intramolecular Nucleophilic Addition of Carbonyl Groups to Alkynes

Zinc‐Catalyzed Tandem Diels–Alder Reactions of Enynals with Alkenes: Generation and Trapping of Cyclic o‐Quinodimethanes (o‐QDMs)

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Rapid Access to Oxabicyclo[2.2.2]octane Skeleton through Cu(I)‐Catalyzed Generation and Trapping of Vinyl‐o‐quinodimethanes (Vinyl‐o‐QDMs)^†

Rapid Access to Oxabicyclo[2.2.2]octane Skeleton through Cu(I)‐Catalyzed Generation and Trapping of Vinyl‐o‐quinodimethanes (Vinyl‐o‐QDMs)^†