A Base‐Mediated Mild Sulfenylation of Indoles and Pyrrole with α‐Acylthiones

Viglianisi, Caterina; Marcantoni, Enrico; Carapacchi, Vanessa; Menichetti, Stefano; Marsili, Laura

doi:10.1002/ejoc.201402894

Cited by 22 publications

(6 citation statements)

References 49 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Commercially available reagents were used as obtained from freshly opened containers without further purification. Aryl selenols 1a-d [32], alkyl selenol 1e [31], and N-thiophthalimides 2 [43][44][45][46][47][48] were prepared according to reported procedures. Spectroscopic data of diselenides 4a-e [26,49] and disulfides 5a-h [30] matched those previously reported in the literature.…”

Section: Methodsmentioning

confidence: 99%

Towards New Catalytic Antioxidants: A Simple and Mild Synthesis of Selenenylsulfides

Tanini¹,

Bonardi²,

Viglianisi³

et al. 2019

Catalysts

Self Cite

View full text Add to dashboard Cite

A new methodology for the synthesis of small molecules containing the S-Se bond is reported. Aryl-and alkyl-selenols react smoothly with N-thiophthalimides to afford the corresponding selenenylsulfides through a clean S N 2 path occurring at the sulfur atom. The reaction proceeds under very mild conditions in DMF in absence of catalysts for most of the substrates. The scope of the reaction was found to be broad, allowing a wide series of selenols and N-thiophtalimides to be efficiently employed in this procedure. Owing to the instability of the S-Se bond, selenenylsulfides exhibited a remarkable tendency to disproportionate to the corresponding symmetric diselenides and disulfides. Preliminary evaluation of the catalytic antioxidant properties of novel selenenylsulfides showed their behaviour as GPx mimics.Catalysts 2019, 9, 333 2 of 11 a second equivalent of GSH, to reform the selenol, together with oxidized glutathione GSSG. The selenenylsulfide, containing the Se-S bridge, represents the key intermediate for the activity of the enzyme [7,[16][17][18][19]. Taking into account the importance of this process, several synthetic approaches to obtain selenated small molecules as enzyme mimics have been developed. However, to the best of our knowledge, a limited number of methods are reported for the preparation of selenenylsulfides. These methods typically exploited the reactivity of diselenides in thiol-diselenide exchange or foresee the reaction of sulfenyl derivatives with thiols [16,17,[20][21][22].It is well established that the Se-S bridge is unstable and undergoes disproportionation reaction to afford diselenides and disulfides. Some examples are reported on selenenylsulfides stabilized by sterically bulky groups or by intramolecular Se . . . Het (N, O) interactions [23].Owing to the interest in these selenium containing compounds, the search for novel procedures to prepare small molecules containing the Se-S unit is of great interest.Our long-dated interest in the chemistry of silyl chalcogenides allowed to disclose novel procedures to access a plethora of sulfur and selenium containing molecules exploiting the nucleophilic behaviour of the chalcogen atom towards various electrophiles [24][25][26][27][28][29]. Recently we reported the reaction of bis(trimethylsilyl)selenide (HMDSS) with N-thiophtalimides as a mild, general metal free procedure for the synthesis of variously substituted disulfides [30].Indeed, despite the interest in the reactivity of selenols as nucleophilic selenium transfer reagents, their use has been critically limited by their instability. However, HMDSS was efficient in the opening of ring strained heterocycles, namely epoxides, episulfides and aziridines, leading to a wide range of β-functionalized selenols, which were stable enough to react with electrophiles under controlled catalytic conditions [31]. Differently substituted stable aryl selenols were also prepared by reduction of the parent diselenides to explore their activity as enzyme inhibitors [32].On the basis of our findings ...

show abstract

Section: Methodsmentioning

confidence: 99%

Towards New Catalytic Antioxidants: A Simple and Mild Synthesis of Selenenylsulfides

Tanini¹,

Bonardi²,

Viglianisi³

et al. 2019

Catalysts

Self Cite

View full text Add to dashboard Cite

show abstract

“…In 2014, Menichetti and co‐workers reported on α‐acylthiones as new sulfenylating reagents obtainable from N ‐thiophthalimides by use of a weak base as promoter (Scheme ) . Sulfenylation of indoles and pyrrole with these α‐acylthiones proceeded efficiently in this system.…”

Section: N‐substituted Succinimides As Sulfenylation Reagentsmentioning

confidence: 99%

Sulfenylation of C–H Bonds for C–S Bond Formation under Metal‐Free Conditions

et al. 2017

View full text Add to dashboard Cite

Sulfenylation of C–H bonds for C–S bond formation under metal‐free conditions has become established as a powerful tool in organic chemistry. Various sulfenylation reagents such as thiols, disulfides, sulfinic acids, and so on have been employed for sulfenynlation reactions. In this review we mainly summarize the recent advances (2014 to the present) in this area and also discuss the mechanisms.

show abstract

“…Organosulfanes play an important role in both chemical and biological processes like total synthesis, medicinal chemistry and material sciences . Moreover, aryl sulfides are essential building blocks for various pharmaceutically important compounds . The incorporation of sulfenyl groups into heterocyclic moieties like indole has garnered much attention because of their wide uses.…”

Section: Introductionmentioning

confidence: 99%

“…The incorporation of sulfenyl groups into heterocyclic moieties like indole has garnered much attention because of their wide uses. Among the various indole derivatives, 3‐sulfenylindoles are significant owing to their potential uses as drugs for the treatment of cancer, heart diseases, allergies, HIV and Alzheimer′s disease (Figure ) . Because of their synthetic importance and diverse pharmacological activities, synthesis of aryl sulfanes represents an important chemical reaction in organic chemistry.…”

Section: Introductionmentioning

confidence: 99%

Sustainable and Site‐Selective C−H Sulfenylation of Aromatic Compounds with Thiol using Catalytic Graphene Oxide and NaI

2017

View full text Add to dashboard Cite

Graphene oxide (GO) in combination with NaI is used as the catalytic system for site‐selective C−H sulfenylation of 1H‐indole, 2‐naphthol, resorcinol and 2‐naphthylamines with thiols. The reaction is usually achieved in the presence of metal catalysts as well as under metal‐free conditions using iodine and a strong oxidizing agent. The present protocol avoids the use of any metal catalysts, strong oxidizing agents and the use of thiols instead of other sulfur‐based reagents making it atom‐economic and environmentally benign. Broader tolerance to functional groups has been tested and a plausible mechanism is proposed. The recovered GO can be recycled without significant loss in catalytic activity up to four runs.

show abstract

A Base‐Mediated Mild Sulfenylation of Indoles and Pyrrole with α‐Acylthiones

Cited by 22 publications

References 49 publications

Towards New Catalytic Antioxidants: A Simple and Mild Synthesis of Selenenylsulfides

Towards New Catalytic Antioxidants: A Simple and Mild Synthesis of Selenenylsulfides

Sulfenylation of C–H Bonds for C–S Bond Formation under Metal‐Free Conditions

Sustainable and Site‐Selective C−H Sulfenylation of Aromatic Compounds with Thiol using Catalytic Graphene Oxide and NaI

Contact Info

Product

Resources

About