Synthesis and photochemistry of 3,6-difluoro-10,11-benzopentacyclo [6,4,0.0,0.0]dodeca-4,10-diene

Kimura, Masao; Kura, Hisatoshi; Nukada, Kaname; Okamoto, Hideki; Satake, Kyosuke; Morosawa, Shiro

doi:10.1039/p19880003307

Cited by 13 publications

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“…The isolated yield of 3 was 16% on the basis of the consumed 2-CN. The structure of the major product ( 4 ) was further confirmed by the triplet sensitization of the irradiated mixture of 2-CN and CHD (Scheme ) …”

Section: Resultsmentioning

confidence: 86%

“…Compounds 1 and 2 can be also formed from the Cope rearrangement of 12 . To explore the existence of 12 , a further irradiation to the photoreaction mixture in the presence of xanthone at −50 to −40 °C was conducted for an additional 4 h (Scheme ) . Similar separatory methods resolved a new product ( 13 ) in 35% yield, as well as 1 and 2 in 18% and 39% yields.…”

Section: Resultsmentioning

confidence: 99%

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Photocycloaddition of Cyanonaphthalenes to 1,3-Cyclohexadiene

Noh

Kim

1998

J. Org. Chem.

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To prevent secondary processes due to facile thermal reaction, low-temperature irradiations of cyanonaphthalenes and 1,3-cyclohexadiene through a Pyrex filter were conducted. Along with the identification of the products, the results of the triplet-sensitized photoreaction of the irradiated mixture, low-temperature 1H NMR study of the irradiated mixture, and the Cope rearrangement reaction of some products suggested that the primary major products are the corresponding exo-[4 + 4] adducts fused at 1,4 position of the naphthalene skeleton and the syn-[2 + 2] adducts fused at 1,2 position. The formations of the primary products in these singlet-state photocycloaddition reactions were interpreted by primary and secondary orbital interactions. A rationalization for the previous results on the photoreactions at room temperature was also provided.

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Section: Resultsmentioning

confidence: 86%

Section: Resultsmentioning

confidence: 99%

Photocycloaddition of Cyanonaphthalenes to 1,3-Cyclohexadiene

Noh

Kim

1998

J. Org. Chem.

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“…Then, xanthone‐sensitized photolysis was conducted. We selected xanthone as the triplet sensitizer because it has been reported that xanthone‐sensitized photolysis effectively promotes intramolecular [π2s + π2s] cycloaddition of [4 + 4]‐type benzene‐naphthalene cross‐dimers . When a 1:1.3 mixture of cage diene 13 and xanthone in degassed acetone‐ d 6 was irradiated at 350 nm, almost no change in its 1 H NMR profile was observed after 1 hour (Figure S1B).…”

Section: Resultsmentioning

confidence: 99%

Synthesis, structure, and photoreactions of fluorinated 2,11‐diaza[3₂]paracyclophane: Photochemical formation of cage‐diene type benzene dimer

Okamoto

Kozai

Okabayashi

et al. 2017

J of Physical Organic Chem

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An octafluorinated 2,11‐diaza[32]paracyclophane derivative 12 was prepared, and its photochemical reaction was investigated. Upon irradiation at 300 nm, the fluorinated azacyclophane 12 underwent efficient photodimerization of the benzene cores to afford the corresponding photoisomer 13, which possessed cage diene benzene dimer structure (pentacyclo[6.4.0.0.2,70.3,1206,9]dodeca‐4,10‐diene skeleton). The cage diene structure was established by single‐crystal X‐ray diffraction analysis. The cage diene 13 thermally isomerized to a syn‐o,o′‐dibenzene isomer 22. The activation parameters for the thermal isomerization were determined to be Ea = 121 kJ mol−1, ΔH≠ = 118 kJ mol−1, ΔS≠(293 K) = 22 J mol−1 K−1, and ΔG≠(293 K) = 111 kJ mol−1. It was revealed that, by photoirradiation at 300 nm, the syn‐o,o′‐dibenzene isomer 22 underwent facile intramolecular [π4s + π4s] cycloaddition to reproduce the cage diene isomer 13.

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“…Photoinduced [4 + 4] reactions represent the highest order photocycoadditions of α-diketone known up to now. [4 + 4] Photocycloadditions have been found in some photoreactions of excited aromatic compounds with dienes [51,52,53,54,55,56,57]. In an isolated example, excited 1,2-naphthoquinone was reported to react with cycloheptatriene to give the [4 + 4] product as minor products [58].…”

Section: Photo-induced Cycloaddition Reactions Of α-Diketonesmentioning

confidence: 99%

Photo-Induced Cycloaddition Reactions of α-Diketones and Transformations of the Photocycloadducts

Huang

Zheng

et al. 2013

Molecules

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Photocycloaddition, along with subsequent transformation of the photocycloadducts, provides expeditious ways to construct various structures. The photoinduced reactions of α-diketones have been reported to proceed via different reaction pathways with the involvement of one or two of the carbonyl groups. Photoinduced reactions of cyclic α-diketones including N-acetylisatin, phenanthrenequinone and isoquinolinetrione with different C=C containing compounds could take place via [2 + 2], [4 + 2] or [4 + 4] photocycloaddition pathways. We have investigated the photoreactions of these cyclic α-diketones with different types of alkenes and alkynes, with a focus on the unusual cascade reactions initiated by the photocycloaddition reactions of these cyclic α-diketones and the applications of these photocycloaddition reactions along with the transformation of the photocycloadducts. In this paper, we discuss the diverse photo-cycloaddition pathways found in the photocycloaddition of o-diones leading to various photocycloadducts and the potential applications of these reactions via further transformation reactions of the adducts.

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Synthesis and photochemistry of 3,6-difluoro-10,11-benzopentacyclo [6,4,0.0,0.0]dodeca-4,10-diene

Cited by 13 publications

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Photocycloaddition of Cyanonaphthalenes to 1,3-Cyclohexadiene

Photocycloaddition of Cyanonaphthalenes to 1,3-Cyclohexadiene

Synthesis, structure, and photoreactions of fluorinated 2,11‐diaza[3₂]paracyclophane: Photochemical formation of cage‐diene type benzene dimer

Photo-Induced Cycloaddition Reactions of α-Diketones and Transformations of the Photocycloadducts

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Synthesis and photochemistry of 3,6-difluoro-10,11-benzopentacyclo [6,4,0.0,0.0]dodeca-4,10-diene

Cited by 13 publications

References 0 publications

Photocycloaddition of Cyanonaphthalenes to 1,3-Cyclohexadiene

Photocycloaddition of Cyanonaphthalenes to 1,3-Cyclohexadiene

Synthesis, structure, and photoreactions of fluorinated 2,11‐diaza[32]paracyclophane: Photochemical formation of cage‐diene type benzene dimer

Photo-Induced Cycloaddition Reactions of α-Diketones and Transformations of the Photocycloadducts

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Synthesis, structure, and photoreactions of fluorinated 2,11‐diaza[3₂]paracyclophane: Photochemical formation of cage‐diene type benzene dimer