Formation of 1,2-dioxanes by electron-transfer photooxygenation of 1,1-disubstituted ethylenes

Gollnick, Klaus; Schnatterer, Albert

doi:10.1016/s0040-4039(01)81277-6

Cited by 44 publications

(6 citation statements)

References 5 publications

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“…This reaction afforded exclusively and quantitatively the cyclic peroxide 5a (Figure 3, S15), by cycloaddition of photochemically produced two radical cations of 5 and one super oxide anion. Similar results under the same conditions have been reported previously [57,58], when DCA was the photosensitizer. Furthermore, upon addition of a small quantity of 1,3,5-trimethoxybenzene, the above reaction, Scheme 7, was retarded.…”

Section: Resultssupporting

confidence: 91%

Surface-Doped Graphitic Carbon Nitride Catalyzed Photooxidation of Olefins and Dienes: Chemical Evidence for Electron Transfer and Singlet Oxygen Mechanisms

et al. 2019

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A new photocatalytic reactivity of carbon-nanodot-doped graphitic carbon nitride (CD-C3N4) with alkenes and dienes, has been disclosed. We have shown that CD-C3N4 photosensitizes the oxidation of unsaturated substrates in a variety of solvents according to two competing mechanisms: the energy transfer via singlet oxygen (1O2) and/or the electron transfer via superoxide (O·−2). The singlet oxygen, derived by the CD-C3N4 photosensitized process, reacts with alkenes to form allylic hydroperoxides (ene products) whereas with dienes, endoperoxides. When the electron transfer mechanism operates, cleavage products are formed, derived from the corresponding dioxetanes. Which of the two mechanisms will prevail depends on solvent polarity and the particular substrate. The photocatalyst remains stable under the photooxidation conditions, unlike the most conventional photosensitizers, while the heterogeneous nature of CD-C3N4 overcomes usual solubility problems.

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Section: Resultssupporting

confidence: 91%

Surface-Doped Graphitic Carbon Nitride Catalyzed Photooxidation of Olefins and Dienes: Chemical Evidence for Electron Transfer and Singlet Oxygen Mechanisms

et al. 2019

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“…The endoperoxide 42a was exclusively produced, as shown in Scheme 51, by the C 60 /SiO 2 or C 60 /Al 2 O 3 ‐photosensitized oxidation of 42 . Similar results (221,222) with these presented in Scheme 51 were reported earlier, when 9,10‐dicyanoanthracene (DCA) was used as the sensitizer.…”

Section: C60‐sensitized Photooxygenationssupporting

confidence: 88%

Singlet Oxygen: Discovery, Chemistry, C₆₀‐Sensitization^†

Orfanopoulos

2021

Photochem & Photobiology

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This review article refers to the discovery of excited molecular oxygen, in particular on its lower singlet excited state ( 1 D g , 1 O 2 ). After a short report on singlet oxygen generation, the review is focused on the chemistry of this reactive species. Specifically, the three major reactions of 1 O 2 with unsaturated organic substrates, namely the [4 + 2] and [2 +2] cycloadditions as well as the ene reaction, are reviewed. The proposed mechanisms of these reactions, through the years, based on experimental and computational work, have been presented. Selected examples of singlet oxygen-synthetic applications are also mentioned. The [60]fullerene and fullereno-materials photosensitized oxidations in homogeneous, as well as in heterogeneous conditions, are also comprehensively discussed.Finally, the self-sensitized photooxidation of open cage fullerenes as well as fullerenes bearing oxidizable groups is reported.

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“…As a synthetic method, the photocatalytic aerobic [2+2+2] cycloaddition of electron‐rich 1,1‐disubstituted styrenes to give 1,2‐dioxanes using 9,10‐dicyanoathracene (DCA) as the photocatalyst was first reported by Gollnick and co‐workers ,,. Synthesis of bicyclic endoperoxides through aerobic [2+2+2] cycloaddition of electron‐rich bis(styrene) substrates was later disclosed by Miyashi and co‐workers, again using DCA as the photocatalyst .…”

Section: Methodsmentioning

confidence: 86%

Visible‐Light Photoredox Catalysis Enables the Biomimetic Synthesis of Nyingchinoids A, B, and D, and Rasumatranin D

et al. 2019

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The total synthesis of nyingchinoids A and B has been achieved through successive rearrangements of a 1,2‐dioxane intermediate that was assembled using a visible‐light photoredox‐catalysed aerobic [2+2+2] cycloaddition. Nyingchinoid D was synthesised with a competing [2+2] cycloaddition. Based on NMR data and biosynthetic speculation, we proposed a structure revision of the related natural product rasumatranin D, which was confirmed through total synthesis. Under photoredox conditions, we observed the conversion of a cyclobutane into a 1,2‐dioxane through retro‐[2+2] cycloaddition followed by aerobic [2+2+2] cycloaddition.

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Formation of 1,2-dioxanes by electron-transfer photooxygenation of 1,1-disubstituted ethylenes

Cited by 44 publications

References 5 publications

Surface-Doped Graphitic Carbon Nitride Catalyzed Photooxidation of Olefins and Dienes: Chemical Evidence for Electron Transfer and Singlet Oxygen Mechanisms

Surface-Doped Graphitic Carbon Nitride Catalyzed Photooxidation of Olefins and Dienes: Chemical Evidence for Electron Transfer and Singlet Oxygen Mechanisms

Singlet Oxygen: Discovery, Chemistry, C₆₀‐Sensitization^†

Visible‐Light Photoredox Catalysis Enables the Biomimetic Synthesis of Nyingchinoids A, B, and D, and Rasumatranin D

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Formation of 1,2-dioxanes by electron-transfer photooxygenation of 1,1-disubstituted ethylenes

Cited by 44 publications

References 5 publications

Surface-Doped Graphitic Carbon Nitride Catalyzed Photooxidation of Olefins and Dienes: Chemical Evidence for Electron Transfer and Singlet Oxygen Mechanisms

Surface-Doped Graphitic Carbon Nitride Catalyzed Photooxidation of Olefins and Dienes: Chemical Evidence for Electron Transfer and Singlet Oxygen Mechanisms

Singlet Oxygen: Discovery, Chemistry, C60‐Sensitization†

Visible‐Light Photoredox Catalysis Enables the Biomimetic Synthesis of Nyingchinoids A, B, and D, and Rasumatranin D

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Singlet Oxygen: Discovery, Chemistry, C₆₀‐Sensitization^†