Photocatalytic oxygenation of olefins with oxygen

Ohkubo, Kei; Nanjo, Takashi; Fukuzumi, Shunichi

doi:10.1016/j.cattod.2006.05.056

Cited by 36 publications

(19 citation statements)

References 62 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…58 3.3 CarbonCarbon Bond Formation via Radical Coupling Using ET State. The photochemical carboncarbon bond formation of aromatic compounds has been extensively investigated not only for synthetic exploitation, but also for basic understanding of the photochemical process.…”

Section: Mesmentioning

confidence: 99%

Rational Design and Functions of Electron Donor–Acceptor Dyads with Much Longer Charge-Separated Lifetimes than Natural Photosynthetic Reaction Centers

Ohkubo

Fukuzumi

2009

Bulletin of the Chemical Society of Japan

Self Cite

115

View full text Add to dashboard Cite

The natural photosynthetic reaction center utilizes sequential multi-step electron transfer from the excited chromophore to the terminal electron acceptor via electron mediators to attain a long lifetime of the final charge-separated (CS) state. Contrary to natural systems, simple electron donoracceptor dyads have been developed to attain a long-lived CS state, where the donor and acceptor molecules are linked with a short spacer. In the case of a directly linked zinc chlorinfullerene dyad, the lifetime of the CS state at ¹150°C is as long as 120 s. This value is the longest CS lifetime ever reported for porphyrin-based donoracceptor linked systems. The use of 9-mesityl-10-methylacridinium ion, which has an extremely long-lived CS state, enables the construction of highly efficient photocatalytic systems such as oxygenation of aromatic compounds and hydrogen evolution.

show abstract

Section: Mesmentioning

confidence: 99%

Rational Design and Functions of Electron Donor–Acceptor Dyads with Much Longer Charge-Separated Lifetimes than Natural Photosynthetic Reaction Centers

Ohkubo

Fukuzumi

2009

Bulletin of the Chemical Society of Japan

Self Cite

115

View full text Add to dashboard Cite

show abstract

“…79 Photocatalytic oxygenation of olefins such as stilbene derivatives also occurs with Acr + -Mes in MeCN and CHCl 3 . 101 In contrast to the case of TPE, the dioxetane intermediates were not detected under the same experimental conditions as employed for TPE. 101 This indicates that the stilbene dioxetanes decompose to the corresponding benzaldehydes spontaneously under the photoirradiation.…”

Section: Of the Mesmentioning

confidence: 88%

Photoinduced Reactions of Radical Ions via Charge Separation

Fukuzumi

Ohkubo

2012

Encyclopedia of Radicals in Chemistry, Biology and Materials

Self Cite

View full text Add to dashboard Cite

This article describes the recent development of photocatalytic reactions using a simple donor‐acceptor‐linked dyad, 9‐mesityl‐10‐methylacridinium ion (Acr + –Mes). The electron‐transfer state of Acr + –Mes (Acr · –Mes ·+ ), produced on visible light irradiation, acts as an efficient oxidant and reductant. The use of Acr + –Mes, which has an extremely long‐lived charge‐separated state, enables the construction of highly efficient photocatalytic systems such as oxygenation, bromination, and carbon‐carbon bond formation of aromatic compounds.

show abstract

“…76 Thus, the electron-transfer oxidation of TPE with the Mes 76 The quantum yield of 1,2-dioxetane increases with an increase in the concentration of TPE to approach a limiting value of 0.17 and 0.022 in CHCl 3 and MeCN, respectively. 77 In general, the most common preparation of 1,2-dioxetanes is through the formal [2 + 2] cycloaddition of singlet oxygen ( 1 O 2 ) to electron-rich alkenes. 78 If alkenes are too electron-poor to react with 1 O 2 , however, no oxygenated products are obtained.…”

Section: Photocatalytic Cycloaddition Of Dioxygenmentioning

confidence: 99%

“…80 It is known that cis-trans isomerization occurs rapidly in the stilbene radical cation. 77 The steady-state cistrans ratio of stilbene has been reported to be 98.8 : 1. 77 The observed yield of trans-stilbene from cis-stilbene was 96% after 60 min of photoirradiation, when the total consumption of cisand trans-stilbene by the photocatalytic oxidation by O 2 was still 4%.…”

Section: Photocatalytic Cycloaddition Of Dioxygenmentioning

confidence: 99%

“…77 The steady-state cistrans ratio of stilbene has been reported to be 98.8 : 1. 77 The observed yield of trans-stilbene from cis-stilbene was 96% after 60 min of photoirradiation, when the total consumption of cisand trans-stilbene by the photocatalytic oxidation by O 2 was still 4%. 77 When anthracene derivatives are used as substrates, Acr + -Mes acts as an efficient photoredox catalyst for the [4 + 2] cycloaddition of O 2 to the anthracene derivatives to afford the corresponding epidioxyanthracenes via radical coupling between the radical cations of the anthracene derivatives and O 2…”

Section: Photocatalytic Cycloaddition Of Dioxygenmentioning

confidence: 99%

See 1 more Smart Citation

Organic synthetic transformations using organic dyes as photoredox catalysts

2014

Self Cite

View full text Add to dashboard Cite

The oxidizing ability of organic dyes is enhanced significantly by photoexcitation. Radical cations of weak electron donors can be produced by electron transfer from the donors to the excited states of organic dyes. The radical cations thus produced undergo bond formation reactions with various nucleophiles. For example, the direct oxygenation of benzene to phenol was made possible under visible-light irradiation of 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) in an oxygen-saturated acetonitrile solution of benzene and water via electron transfer from benzene to the triplet excited state of DDQ. 3-Cyano-1-methylquinolinium ion (QuCN(+)) can also act as an efficient photocatalyst for the selective oxygenation of benzene to phenol using oxygen and water under homogeneous and ambient conditions. Alkoxybenzenes were also obtained when water was replaced by alcohol under otherwise identical experimental conditions. QuCN(+) can also be an effective photocatalyst for the fluorination of benzene with O2 and fluoride anion. Photocatalytic selective oxygenation of aromatic compounds was achieved using an electron donor-acceptor-linked dyad, 9-mesityl-10-methylacridinium ion (Acr(+)-Mes), as a photocatalyst and O2 as the oxidant under visible-light irradiation. The electron-transfer state of Acr(+)-Mes produced upon photoexcitation can oxidize and reduce substrates and dioxygen, respectively, leading to the selective oxygenation and halogenation of substrates. Acr(+)-Mes has been utilized as an efficient organic photoredox catalyst for many other synthetic transformations.

show abstract

Photocatalytic oxygenation of olefins with oxygen

Cited by 36 publications

References 62 publications

Rational Design and Functions of Electron Donor–Acceptor Dyads with Much Longer Charge-Separated Lifetimes than Natural Photosynthetic Reaction Centers

Rational Design and Functions of Electron Donor–Acceptor Dyads with Much Longer Charge-Separated Lifetimes than Natural Photosynthetic Reaction Centers

Photoinduced Reactions of Radical Ions via Charge Separation

Organic synthetic transformations using organic dyes as photoredox catalysts

Contact Info

Product

Resources

About