Metal- and photocatalyst-free synthesis of 3-selenylindoles and asymmetric diarylselenides promoted by visible light

Lemir, Ignacio D.; Castro‐Godoy, Willber D.; Heredia, Adrián A; Schmidt, Luciana C.; Argüello, Juan E.

doi:10.1039/c9ra03642c

Cited by 48 publications

(29 citation statements)

References 74 publications

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“…[15] In an alternative approach, the addition of phenylselenium cation (PhSe + ) to in-situ formed cyclohexenol and subsequently oxidative aromatization afforded ortho-phenylselenium substituted phenols. [16] Electrophilic addition of phenylselenenium ion (PhSe + ) to phenol has been studied by Henriksen under oxidative conditions in which 2,6-bis(phenyl-seleno)phenol 19 was proposed an intermediate in the reaction for the synthesis of 2,6-bis(phenylseleno)-1,4-benzoquinone. [15a-b] Here, phenols not only with electron-withdrawing or donating group but also CHO and CN sensitive functionalities have been tolerated under the copper-catalyzed reaction conditions.…”

Section: Resultsmentioning

confidence: 99%

“…[13] Moreover, to the best of our knowledge, the installation of two arylseleno groups into phenols has not been reported to date despite the various reports on the synthesis of organoselenides. [14][15][16][17] Here, in continuation of our work on the synthesis of organochalcogen compounds, [12,15c,d] we present a copper-catalyzed synthesis of bis-phenylselenide phenols and synthesis and crystal structures of tris selenium substituted phenols have also been presented. The radical quenching, singlet oxygen quenching, and peroxide decomposing antioxidant activity of the synthesized bis and tris selenol-bisphenols have been explored by DPPH assay.…”

Section: Introductionmentioning

confidence: 99%

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Radical Chain Breaking Bis(ortho‐organoselenium) Substituted Phenolic Antioxidants

Upadhyay

Bhakuni

Meena

et al. 2021

Chemistry An Asian Journal

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The presence of a chalcogen atom at the orthoposition of phenols enhances their radical chain-breaking activity. Here, a copper(I)-catalyzed reaction of 2,6-dibromoand 2,6-diiodophenols with diorganodiselenides has been studied for the introduction of two organoselenium substituents at both ortho-positions of the phenolic radical chainbreaking antioxidants, which afforded 2,6-diorganoselenosubstituted phenols in 80-92% yields having electron-donating CH 3 , and electron-withdrawing CN and CHO functionalities. Additionally, 2,6-diiodophenols with electron-withdrawing CHO and CN groups also afforded novel 5,5'selenobis(4-hydroxy-3-(phenylselanyl)benzaldehyde) and 5,5'selenobis(4-hydroxy-3-(phenylselanyl)benzonitrile) consisting of three selenium and two phenolic moieties along with 2,6diorganoseleno-substituted phenols has been synthesized. The electron-withdrawing CHO group has been reduced by sodium borohydride to the electron-donating alcohol CH 2 OH group, which is desirable for efficient radical quenching activity of phenols. The developed copper-catalyzed reaction conditions enable the installation of two-arylselenium group ortho to phenolic radical chain-breaking antioxidants, which may not be possible by conventional organolithium-bromine exchange methods due to the sluggish reactivity of trianions (dicarba and phenoxide anion), which are generated by the reaction of organolithium with 2,6-dibromophenols, with diorganodiselenides. The antioxidant activities of the synthesized bis and tris selenophenols have been accessed by DPPH, thiol peroxides, and singlet oxygen quenching assay. The radical quenching antioxidant activity has been studied for the synthesized compounds by 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay. The bis-selenophenols show comparable radical deactivating activity, while tris seleno-bisphenols show higher radical deactivating activity than α-tocopherol. Furthermore, the tris seleno-bisphenol shows comparable peroxide decomposing activity with ebselen molecules.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Radical Chain Breaking Bis(ortho‐organoselenium) Substituted Phenolic Antioxidants

Upadhyay

Bhakuni

Meena

et al. 2021

Chemistry An Asian Journal

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“…To investigate the probable mechanistic pathway for the present reaction, an on/off visible light photo‐irradiation experiments were performed using 1 mmol of each dimedone ( 1 ), phenacyl bromide ( 2a ), and aniline ( 3 ) in 5 ml aqueous ethanol (1:1) under the illumination of 22 W CFL on a magnetic stirrer at room temperature. The observed results lead us to draw most probable mechanism of the synthesized products (Figure 2) [26(a),28].…”

Section: Resultsmentioning

confidence: 99%

A metal‐free visible light promoted three‐component facile synthesis of 4‐oxo‐tetrahydroindoles in ethanol–water

Ansari

Nazeef

Ali

et al. 2020

Journal of Heterocyclic Chem

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A mild and efficient visible light–mediated one‐pot multicomponent tandem approach to construct 4‐oxo‐tetrahydroindoles in ethanol–water medium at room temperature has been described. The characteristics of reported methodology are the utilization of visible light, an ideal source of energy to generate CC and CN bonds from commercially available substrates namely dimedone, phenacyl bromides, and amines. The presented protocol is highly compatible for developing 4‐oxo‐tetrahydroindole derivatives with improved selectivity and high yields. Moreover, metal‐free synthesis, environmental friendly solvent, easy workup process, high atom economy, cost‐effectiveness, short reaction time, and broad substratescope are the major advantages of reported protocol.

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“…An alternative methodology for the direct selenylation of indoles and few activated arenes 20 was later described by Argüello, applying ethanol as a sustainable solvent under blue LED irradiation (Scheme 2). The protocol is carried out under air atmosphere and provides different types of selenylated indoles, N,N‐ dimethylaniline, phloroglucinol and thiazoles, in satisfactory yields [20] . In this transformation, the authors propose three possible pathways.…”

Section: Selenylation Of (Hetero)arenesmentioning

confidence: 99%

Light‐Mediated Seleno‐Functionalization of Organic Molecules: Recent Advances

Rafique

Rampon

Azeredo

et al. 2021

The Chemical Record

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Organoselenium compounds constitute an important class of substances with applications in the biological, medicinal and material sciences as well as in modern organic synthesis, attracting considerable attention from the scientific community. Therefore, the construction of the C−Se bond via facile, efficient and sustainable strategies to access complex scaffolds from simple substrates are an appealing and hot topic. Visible light can be regarded as an alternative source of energy and is associated with environmentally‐friendly processes. Recently, the use of visible‐light mediated seleno‐functionalization has emerged as an ideal and powerful route to obtain high‐value selenylated products, with diminished cost and waste. This approach, involving photo‐excited substrates/catalyst and single‐electron transfer (SET) between substrates in the presence of visible light has been successfully used in the versatile and direct insertion of organoselenium moieties in activated and unactivated C(sp3)−H, C(sp2)−H, C(sp)−H bonds as well as C−heteroatom bonds. In most cases, ease of operation and accessibility of the light source (LEDs or commercial CFL bulbs) makes this approach more attractive and sustainable than the traditional strategies.

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Metal- and photocatalyst-free synthesis of 3-selenylindoles and asymmetric diarylselenides promoted by visible light

Abstract: A novel and sustainable procedure for the synthesis of 3-selenylindoles employing diorganyl diselenides and indoles or electron-rich arenes and promoted by visible light was developed.

Cited by 48 publications

References 74 publications

Radical Chain Breaking Bis(ortho‐organoselenium) Substituted Phenolic Antioxidants

Radical Chain Breaking Bis(ortho‐organoselenium) Substituted Phenolic Antioxidants

A metal‐free visible light promoted three‐component facile synthesis of 4‐oxo‐tetrahydroindoles in ethanol–water

Light‐Mediated Seleno‐Functionalization of Organic Molecules: Recent Advances

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