Visible-light photocatalytic aerobic oxidation of sulfides to sulfoxides with a perylene diimide photocatalyst

Gao, Yueying; Xu, Huan; Zhang, Shiwei; Zhang, Yan; Tang, Chunlei; Fan, Weizheng

doi:10.1039/c9ob00945k

Cited by 54 publications

(32 citation statements)

References 88 publications

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“…As the oxidation of thioanisole can involve either singlet oxygen ( 1 O 2 ), the superoxide radical anion (O 2 * À ) or both 1 O 2 and O 2 * À , [36,[42][43][44][45] chemical trapping experiments were performed to investigate the reaction mechanism. Control reactions in the presence of a singlet oxygen trapping agent [36,46] resulted in greatly reduced thioanisole 10 oxidation, confirming that 1 O 2 is involved in the reaction mechanism for both BDP 1 and Ir(I)-BDP SS 3 (Figure 3 and Table S7).…”

Section: Resultsmentioning

confidence: 99%

Understanding the Synergistic Effects Observed When Using Tethered Dual Catalysts for Heat and Light Activated Catalysis

et al. 2020

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Dual catalysis, where two different catalysts work cooperatively to promote a chemical reaction, is an important synthetic approach as it can allow a wide range of unique reactivity to be accessed. Whilst most dual catalysis strategies utilise separate catalysts in the reaction mixture, there is a growing interest in using tethered dual catalysts to increase cooperativity between the catalytic centres. In this current work we sought to determine the origin of the catalytic synergy observed for a series of Ir(I) based complexes tethered to a BODIPY type photocatalyst through different tethering modes. Kinetic analyses revealed that the tethered dual catalysts were more effective at promoting heat activated intermolecular hydro-amination than the un-tethered analogues. The tethering mode had a significant influence on the magnitude of this synergistic enhancement observed for the hydroamination reaction, likely due to a combination of steric and electronic ligand effects. Investigations into the effect of the tethered dual catalysts on the light activated oxidation of thioanisole demonstrated that chemical tethering leads to substantial increases in photocatalytic activity, which was once again impacted by the tethering mode. The origin of the observed enhancement was found to be due to both increased singlet oxygen generation through the heavy atom effect, as well as direct involvement of the Ir centre in the oxidation reaction pathway.

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Section: Resultsmentioning

confidence: 99%

Understanding the Synergistic Effects Observed When Using Tethered Dual Catalysts for Heat and Light Activated Catalysis

et al. 2020

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“…In 2019, Zhang and Fan investigated the use of a perylene diimide dye for the photochemical aerobic oxidation of sulfides (Scheme 10, B). [26] Perylene diimide 17 was found to be capable of successfully oxidizing a wide variety of sulfides, namely thioanisole derivatives, alkyl aryl sulfides bearing an allyl or cyclopropyl group, diphenyl, dibenzyl and dialkyl sulfides. [26] It was mentioned that electron-deficient aryl groups, orthosubstituted as well as diphenyl substrates, required longer reaction times, while dialkyl sulfides were oxidized faster.…”

Section: Dyesmentioning

confidence: 99%

“…[26] Perylene diimide 17 was found to be capable of successfully oxidizing a wide variety of sulfides, namely thioanisole derivatives, alkyl aryl sulfides bearing an allyl or cyclopropyl group, diphenyl, dibenzyl and dialkyl sulfides. [26] It was mentioned that electron-deficient aryl groups, orthosubstituted as well as diphenyl substrates, required longer reaction times, while dialkyl sulfides were oxidized faster. The method was also applied in the synthesis of the bioactive sulfoxide 18, which is a potent CDK2 inhibitor.…”

Section: Dyesmentioning

confidence: 99%

“…In 2019, Zhang and Fan investigated the use of a perylene diimide dye for the photochemical aerobic oxidation of sulfides (Scheme 10, B ) [26] . Perylene diimide 17 was found to be capable of successfully oxidizing a wide variety of sulfides, namely thioanisole derivatives, alkyl aryl sulfides bearing an allyl or cyclopropyl group, diphenyl, dibenzyl and dialkyl sulfides [26] . It was mentioned that electron‐deficient aryl groups, ortho ‐substituted as well as diphenyl substrates, required longer reaction times, while dialkyl sulfides were oxidized faster.…”

Section: Organic Photocatalysismentioning

confidence: 99%

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Aerobic Photocatalysis: Oxidation of Sulfides to Sulfoxides

2022

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Sulfoxides constitute one of the most important functional groups in organic chemistry found in numerous pharmaceuticals and natural products. Sulfoxides are usually obtained from the oxidation of the corresponding sulfides. Among various oxidants, oxygen or air are considered the greenest and most sustainable reagent. Photochemistry and photocatalysis is increasingly applied in new, as well as traditional, yet demanding, reaction, like the aerobic oxidation of sulfides to sulfoxides, since photocatalysis has provided the means to access them in mild and effective ways. In this review, we will summarize the photochemical protocols that have been developed for the oxidation of sulfides to sulfoxides, employing air or oxygen as the oxidant. The aim of this review is to present: i) a historical overview, ii) the key mechanistic studies and proposed mechanisms and iii) categorize the different catalytic systems in literature.Scheme 2. Traditional sulfide oxidation methods. Scheme 3. Sulfide oxidation methods utilizing oxygen as the oxidant.

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“…[41,42] In this regard, Zhang, Fan, and co-workers reported the aerobic oxidation of sulfides 5 to sulfoxides 6 by means of the photochemical activity of A under blue light irradiation ( Figure 5). [43] This relevant transformation has practical application in the preparation of valuable biologically active sulfoxide derivatives. [44] Remarkably, the authors found that two different reaction mechanism could be operative.…”

Section: Oxidation Of Sulfidesmentioning

confidence: 99%

Use of Perylene Diimides in Synthetic Photochemistry

2021

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Dedicated to Professor Franco Cozzi on the occasion of his 70th birthday. Perylene diimides (PDIs) are valuable organic chromophores that stand out for their outstanding optical and redox properties. Owing to these features, PDIs have emerged as prominent dyes capable of acting as photocatalysts for numerous relevant organic transformations. This Minireview highlights the recent advances in the application of PDIs in organic photocatalysis. The various mechanistic pathways of the photo-reduction reaction of aryl halides, recently proposed in independent studies, are discussed with an eye to unsolved challenges and forward-looking opportunities regarding the use of PDIs within this field.

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Visible-light photocatalytic aerobic oxidation of sulfides to sulfoxides with a perylene diimide photocatalyst

Abstract: Under visible light, a metal-free aerobic selective sulfoxidation photosensitized by a perylene diimide photocatalyst has been developed.

Cited by 54 publications

References 88 publications

Understanding the Synergistic Effects Observed When Using Tethered Dual Catalysts for Heat and Light Activated Catalysis

Understanding the Synergistic Effects Observed When Using Tethered Dual Catalysts for Heat and Light Activated Catalysis

Aerobic Photocatalysis: Oxidation of Sulfides to Sulfoxides

Use of Perylene Diimides in Synthetic Photochemistry

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