Photocatalytic Aerobic Epoxidation of Alkenes under Visible Light Irradiation by an Iron(III) Porphyrin with Mg–Al Hydrotalcite Anionic Clay

Teramura, Kentaro; Ogura, Kentaro; Sugimoto, Takashi; Tsuneoka, Hideo; Shishido, Tetsuya; Tanaka, Tsunehiro

doi:10.1246/cl.2009.1098

Cited by 7 publications

(3 citation statements)

References 11 publications

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“…Photocatalysis is a hot research area in the field of oxidation 17,41,42 .

{normalO}_{2}^{\cdot -}

was always generated in photocatalytic system, 43 such as using 2‐phenyl‐4‐(1‐naphthyl)quinolinium ion, 44 9‐mesityl‐10‐methylacridinium 45 and g ‐C 3 N 4 46 as the photocatalysts.…”

Section: Resultsmentioning

confidence: 99%

A DFT and kinetic study: Is it possible to prepare epoxides without catalysts using the in‐situ generated peroxy radicals or peroxides by one‐step method?

Kang

Gao

et al. 2023

J Comput Chem

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DFT calculations and kinetic analysis have been employed to comprehensively explore the possibility to prepare epoxides by one‐step method using the in‐situ generated peroxy radicals or hydroperoxides as epoxidizing agents. Computational studies demonstrated that the selectivities for the reaction systems of O2/R2/R1, O2/CuH/R1, O2/CuH/styrene, O2/AcH/R1 were 68.2%, 69.6%, 100% and 93.3%, respectively. The in‐situ generated peroxide radicals, such as HOO˙, CuOO˙ and AcOO˙, could react with R1 or styrene by attacking the CC double bond to form a CO bond and subsequently undergoing a cleavage of OO bond to yield epoxides. Peroxide radicals could abstract a hydrogen atom from methyl group on R1, forming unwanted by‐products. It should be noted that the hydrogen atoms of HOO˙ is easy to be abstracted by CC double bond and simultaneously the oxygen atom is connected to the CH moiety to form an alkyl peroxy radical (Rad11), greatly limiting the selectivity. The comprehensive mechanistic studies provide a deep understanding on preparing epoxides by one‐step method.

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“…Photocatalysis is a hot research area in the field of oxidation 17,41,42 .

{normalO}_{2}^{\cdot -}

Section: Resultsmentioning

confidence: 99%

A DFT and kinetic study: Is it possible to prepare epoxides without catalysts using the in‐situ generated peroxy radicals or peroxides by one‐step method?

Kang

Gao

et al. 2023

J Comput Chem

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“…Using molecular oxygen as an oxidant is a longstanding strategic subject, − and significant achievements in aerobic epoxidation have been made. − Nevertheless, most reports − have used metallic compounds/additives or metallic catalysts/coreductants (such as Et 2 Zn/amino alcohol, Co(II)TPP-OCH 3 /isobutyraldehyde, and Mn(TPP)OAc/isobutyraldehyde) (Scheme a), which always lead to metal residue and poor atom economy. Only a limited number of reports , related to the catalytic epoxidation of α,β-unsaturated ketones with molecular oxygen as the oxidant in the absence of metallic compounds have been reported.…”

Section: Introductionmentioning

confidence: 99%

Visible Light-Induced Aerobic Epoxidation of α,β-Unsaturated Ketones Mediated by Amidines

Zhou

Meng

et al. 2018

J. Org. Chem.

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An aerobic photoepoxidation of α,β-unsaturated ketones driven by visible light in the presence of tetramethylguanidine (3b), tetraphenylporphine (H 2 TPP), and molecular oxygen under mild conditions was revealed. The corresponding α,β-epoxy ketones were obtained in yields of up to 94% in 96 h. The reaction time was shortened to 4.6 h by flow synthesis. The mechanism related to singlet oxygen was supported by experiments and density functional theory (DFT) calculations.

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“…[11] We also determined that the selective photocatalytic oxidation of alcohols [12] and amines [13] [14] Solid bases such as MgO, CaO, and ZnO enhanced the conversion of cyclohexene to 1,2-epoxycyclohexane with high selectivity, whereas amphoteric metal oxides such as Al 2 …”

Section: Introductionmentioning

confidence: 99%

Photoactivation of Molecular Oxygen by an Iron(III) Porphyrin with a Magnesium Aluminum Layered Double Hydroxide for the Aerobic Epoxidation of Cyclohexene

et al. 2014

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The photocatalytic aerobic epoxidation of cyclohexene proceeded under visible‐light irradiation only if 5,10,15,20tetrakis(pentafluorophenyl)porphyrin iron(III) chloride ([FeIII(TPFPP)Cl]) was combined with Mg‐Al layered double hydroxide (Mg‐Al LDH) as a solid base in chloroform. The OH groups in the Mg‐Al LDH exchanged with the axial Cl ligands in [FeIII(TPFPP)Cl] to afford [FeIII(TPFPP)OH], which functioned photocatalytically in the presence of Mg‐Al LDH but was inactive in its absence. The band in the action spectrum agreed well with the Soret band in the UV/Vis absorption spectrum of [FeIII(TPFPP)OH]. The spectral changes indicated the reduction of [FeIII(TPFPP)OH] to [FeII(TPFPP)] under visible‐light irradiation, which in turn activates O2 that could be used for the epoxidation of cyclohexene.

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Photocatalytic Aerobic Epoxidation of Alkenes under Visible Light Irradiation by an Iron(III) Porphyrin with Mg–Al Hydrotalcite Anionic Clay

Cited by 7 publications

References 11 publications

A DFT and kinetic study: Is it possible to prepare epoxides without catalysts using the in‐situ generated peroxy radicals or peroxides by one‐step method?

A DFT and kinetic study: Is it possible to prepare epoxides without catalysts using the in‐situ generated peroxy radicals or peroxides by one‐step method?

Visible Light-Induced Aerobic Epoxidation of α,β-Unsaturated Ketones Mediated by Amidines

Photoactivation of Molecular Oxygen by an Iron(III) Porphyrin with a Magnesium Aluminum Layered Double Hydroxide for the Aerobic Epoxidation of Cyclohexene

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