Molecules

Research

Jump to: Review

13 pages, 1767 KiB

Open AccessArticle

Modulation of Properties in [1]Benzothieno[3,2-b][1]benzothiophene Derivatives through Sulfur Oxidation

by Aneta Rzewnicka, Rafał Dolot, Maciej Mikina, Jerzy Krysiak and Remigiusz Żurawiński

Molecules 2024, 29(15), 3575; https://doi.org/10.3390/molecules29153575 - 29 Jul 2024

Viewed by 706

Abstract

This study explores the impact of sulfur oxidation on the structural, optical, and electronic properties of [1]benzothieno[3,2-b][1]benzothiophene (BTBT) derivatives, specifically focusing on 2,7-dibromo BTBT (2,7-diBr-BTBT) and its oxidized forms, 5,5-dioxide (2,7-diBr-BTBTDO) and 5,5,10,10–tetraoxide (2,7-diBr-BTBTTO [...] Read more.

This study explores the impact of sulfur oxidation on the structural, optical, and electronic properties of [1]benzothieno[3,2-b][1]benzothiophene (BTBT) derivatives, specifically focusing on 2,7-dibromo BTBT (2,7-diBr-BTBT) and its oxidized forms, 5,5-dioxide (2,7-diBr-BTBTDO) and 5,5,10,10–tetraoxide (2,7-diBr-BTBTTO). The bromination of BTBT followed by sequential oxidation with m-chloroperoxybenzoic acid yielded the target compounds in good yields. They were characterized using a wide array of analytical techniques including different spectroscopic methods, X-ray analysis, thermal analysis, and quantum chemical calculations. The results revealed that sulfur oxidation significantly alters the crystal packing, thermal stability, and optoelectronic properties of BTBT derivatives. Notably, the oxidized forms exhibited increased thermal stability and enhanced emission properties, with quantum yields exceeding 99%. These findings provide valuable insights for designing advanced organic semiconductors and fluorescent materials with tunable properties, based on the BTBT core. Full article

(This article belongs to the Special Issue Organosulfur and Organoselenium Chemistry)

► Show Figures

Figure 1

14 pages, 3139 KiB

Open AccessArticle

Oxysulfonylation of Alkynes with Sodium Sulfinates to Access β-Keto Sulfones Catalyzed by BF₃·OEt₂

by Shi-Wei Yu, Zu-Jia Chen, Huan-Qing Li, Wen-Xi Li, Yun Li, Zong Li and Zhao-Yang Wang

Molecules 2024, 29(15), 3559; https://doi.org/10.3390/molecules29153559 - 28 Jul 2024

Viewed by 653

Abstract

An efficient and operationally simple method for the synthesis of β-keto sulfones through the BF₃·OEt₂-promoted reaction of alkynes and sodium sulfinates is developed. With its facile and selective access to the targets, it features good functional group compatibility, mild [...] Read more.

An efficient and operationally simple method for the synthesis of β-keto sulfones through the BF₃·OEt₂-promoted reaction of alkynes and sodium sulfinates is developed. With its facile and selective access to the targets, it features good functional group compatibility, mild conditions, easily available starting materials, and good yields. Notably, the reaction does not require metal catalysts or chemical reagents with pungent odors. Full article

(This article belongs to the Special Issue Organosulfur and Organoselenium Chemistry)

► Show Figures

Figure 1

12 pages, 1680 KiB

Open AccessArticle

Bismuth(III)-Catalyzed Regioselective Selenation of Indoles with Diaryl Diselenides: Synthesis of 3-Selanylindoles

by Mio Matsumura, Airi Umeda, Yuika Sumi, Naoki Aiba, Yuki Murata and Shuji Yasuike

Molecules 2024, 29(13), 3227; https://doi.org/10.3390/molecules29133227 - 8 Jul 2024

Viewed by 598

Abstract

Heterocyclic aryl selenides have recently attracted considerable research interest owing to their applications in biological and pharmaceutical fields. Herein, we describe a simple and general synthesis of 3-selanylindoles via a novel regioselective C–H selenation of indoles using a bismuth reagent as a catalyst. [...] Read more.

Heterocyclic aryl selenides have recently attracted considerable research interest owing to their applications in biological and pharmaceutical fields. Herein, we describe a simple and general synthesis of 3-selanylindoles via a novel regioselective C–H selenation of indoles using a bismuth reagent as a catalyst. The reactions of indoles with diselenides in the presence of 10 mol% BiI₃ at 100 °C in DMF afforded the corresponding 3-selanylindoles in moderate-to-excellent yields. The reaction proceeded efficiently under aerobic conditions by adding only a catalytic amount of BiI₃, which was non-hygroscopic and less toxic, and both selanyl groups of the diselenide were transferred to the desired products. Full article

(This article belongs to the Special Issue Organosulfur and Organoselenium Chemistry)

► Show Figures

Graphical abstract

12 pages, 1644 KiB

Open AccessArticle

Iron-Catalyzed Sulfonylmethylation of Imidazo[1,2-α]pyridines with N,N-Dimethylacetamide and Sodium Sulfinates

by Shengnan Sun, Hexia Ye, Haibo Liu, Junchen Li and Xiaojing Bi

Molecules 2024, 29(13), 3196; https://doi.org/10.3390/molecules29133196 - 5 Jul 2024

Viewed by 543

Abstract

Functionalized imidazo[1,2-α]pyridines are important scaffolds in pharmaceuticals. Herein, we present an efficient 3-sulfonylmethylation protocol for imidazo[1,2-α]pyridines by sodium sulfinates in DMA and H₂O (2:1) via an FeCl₃-catalyzed three-component coupling reaction. Various sulfonylmethyl imidazo[1,2-α]pyridines were thus afforded in high yields [...] Read more.

Functionalized imidazo[1,2-α]pyridines are important scaffolds in pharmaceuticals. Herein, we present an efficient 3-sulfonylmethylation protocol for imidazo[1,2-α]pyridines by sodium sulfinates in DMA and H₂O (2:1) via an FeCl₃-catalyzed three-component coupling reaction. Various sulfonylmethyl imidazo[1,2-α]pyridines were thus afforded in high yields with excellent functional group tolerance. A plausible oxidation-addition mechanism was proposed. Full article

(This article belongs to the Special Issue Organosulfur and Organoselenium Chemistry)

► Show Figures

Graphical abstract

18 pages, 2520 KiB

Open AccessArticle

Upper Rim-Bridged Calix[4]arenes via Cyclization of meta Alkynyl Intermediates with Diphenyl Diselenide

by Anastasia Surina, Karolína Salvadori, Matěj Poupě, Jan Čejka, Ludmila Šimková and Pavel Lhoták

Molecules 2024, 29(6), 1237; https://doi.org/10.3390/molecules29061237 - 11 Mar 2024

Viewed by 930

Abstract

A Sonogashira coupling of meta-iodocalix[4]arene with various terminal acetylenes confirmed that the meta position of calixarene is well addressable, and that both thermal and microwave protocols led to good yields of alkynylcalixarenes. Alkynes thus obtained were subjected to the ferric chloride and [...] Read more.

A Sonogashira coupling of meta-iodocalix[4]arene with various terminal acetylenes confirmed that the meta position of calixarene is well addressable, and that both thermal and microwave protocols led to good yields of alkynylcalixarenes. Alkynes thus obtained were subjected to the ferric chloride and diphenyl diselenide-promoted electrophilic closure. It turns out that the calix[4]arenes give completely different bridging products than those described for the non-macrocyclic starting compounds. This can be demonstrated not only by the isolation of products with a six-membered ring (6-exo-dig), but mainly by the smooth formation of the 5-endo-dig cyclization, which has never been observed in the aliphatic series. An attempt at electrocyclization led to a high yield of the 1,2-diketone (oxidation of the starting alkyne), again in contrast to the reaction described for the acyclic derivatives. The structures of the unexpected products were unequivocally established by X-ray analysis and clearly demonstrate how the preorganized macrocyclic skeleton favors a completely different regioselectivity of cyclization reactions compared to common aliphatic compounds. Full article

(This article belongs to the Special Issue Organosulfur and Organoselenium Chemistry)

► Show Figures

Graphical abstract

13 pages, 1000 KiB

Open AccessArticle

Selenium Biofortification Effect on Glucosinolate Content of Brassica oleracea var. italic and Eruca vesicaria

by Azra Đulović, Katarina Usanović, Lea Kukoč Modun and Ivica Blažević

Molecules 2023, 28(20), 7203; https://doi.org/10.3390/molecules28207203 - 21 Oct 2023

Cited by 3 | Viewed by 1116

Abstract

Glucosinolates (GSLs) in different plant parts of broccoli (Brassica oleracea var. italic) and rocket (Eruca vesicaria) were analyzed qualitatively and quantitatively before and after treatment with sodium selenate (2 and 5 mM), by their desulfo-counterparts using the UHPLC-DAD-MS/MS technique. [...] Read more.

Glucosinolates (GSLs) in different plant parts of broccoli (Brassica oleracea var. italic) and rocket (Eruca vesicaria) were analyzed qualitatively and quantitatively before and after treatment with sodium selenate (2 and 5 mM), by their desulfo-counterparts using the UHPLC-DAD-MS/MS technique. Twelve GSLs were detected in broccoli (five aliphatic, one arylaliphatic, and six indolic), where 4-(methylsulfanyl)butyl GSL (glucoerucin) was the main one in the roots (4.88–9.89 µmol/g DW), 4-(methylsulfinyl)butyl GSL (glucoraphanin) in stems (0.44–1.11 µmol/g DW), and 4-hydroxyindol-3-ylmethyl GSL (4-hydroxyglucobrassicin) in leaves (0.51–0.60 µmol/g DW). No GSL containing selenium was detected in the treated broccoli. Ten GSLs were detected in rocket (seven aliphatic and three indolic), where 4-(methylsulfanyl)butyl GSL (glucoerucin) was the main one in the roots (4.50–20.59 µmol/g DW) and 4-methoxyindol-3-ylmethyl GSL (4-methoxyglucobrassicin) in the aerial part (0.57–5.69 µmol/g DW). As a result of induced stress by selenium fertilization, the total GSL content generally increased in both plants. In contrast to broccoli, the roots and the aerial part of the rocket treated with a high concentration of sodium selenate contained 4-(methylseleno)butyl GSL (glucoselenoerucin) (0.36–4.48 µmol/g DW). Although methionine-derived GSLs are the most abundant in both plants, the plants’ ability to tolerate selenate and its regulation by selenoglucosinolate production is species- and growth-stage-dependent. Full article

(This article belongs to the Special Issue Organosulfur and Organoselenium Chemistry)

► Show Figures

Figure 1

Review

Jump to: Research

20 pages, 3986 KiB

Open AccessReview

An Examination of Chemical Tools for Hydrogen Selenide Donation and Detection

by Rynne A. Hankins and John C. Lukesh

Molecules 2024, 29(16), 3863; https://doi.org/10.3390/molecules29163863 - 15 Aug 2024

Viewed by 328

Abstract

Hydrogen selenide (H₂Se) is an emerging biomolecule of interest with similar properties to that of other gaseous signaling molecules (i.e., gasotransmitters that include nitric oxide, carbon monoxide, and hydrogen sulfide). H₂Se is enzymatically generated in humans where it serves [...] Read more.

Hydrogen selenide (H₂Se) is an emerging biomolecule of interest with similar properties to that of other gaseous signaling molecules (i.e., gasotransmitters that include nitric oxide, carbon monoxide, and hydrogen sulfide). H₂Se is enzymatically generated in humans where it serves as a key metabolic intermediate in the production of selenoproteins and other selenium-containing biomolecules. However, beyond its participation in biosynthetic pathways, its involvement in cellular signaling or other biological mechanisms remains unclear. To uncover its true biological significance, H₂Se-specific chemical tools capable of functioning under physiological conditions are required but lacking in comparison to those that exist for other gasotransmitters. Recently, researchers have begun to fill this unmet need by developing new H₂Se-releasing compounds, along with pioneering methods for selenide detection and quantification. In combination, the chemical tools highlighted in this review have the potential to spark groundbreaking explorations into the chemical biology of H₂Se, which may lead to its branding as the fourth official gasotransmitter. Full article

(This article belongs to the Special Issue Organosulfur and Organoselenium Chemistry)

► Show Figures

Figure 1

19 pages, 10172 KiB

Open AccessReview

Synthesis of Thionated Perylenediimides: State of the Art and First Investigations of an Alternative to Lawesson’s Reagent

by Oksana Kharchenko, Anna Hryniuk, Oksana Krupka and Piétrick Hudhomme

Molecules 2024, 29(11), 2538; https://doi.org/10.3390/molecules29112538 - 28 May 2024

Viewed by 685

Abstract

Perylenediimides (PDIs) are composed of a central perylene ring, on which are grafted two imide groups at the peri positions. Thionated PDIs are characterized by the substitution of one or more oxygen atoms of these imide functions with sulfur atoms. This structural modification [...] Read more.

Perylenediimides (PDIs) are composed of a central perylene ring, on which are grafted two imide groups at the peri positions. Thionated PDIs are characterized by the substitution of one or more oxygen atoms of these imide functions with sulfur atoms. This structural modification alters the electronic properties with a redshift of the optical absorption accompanied by modification of the charge transport characteristics compared to their non-thionated counterparts. These properties make them suitable candidates for applications in optoelectronic devices, such as organic light-emitting diodes and organic photovoltaics. Moreover, the presence of sulfur atom(s) can favor the promotion of reactive oxygen species production for photodynamic and photothermal therapies. These thionated PDIs can be synthesized through the post-functionalization of PDIs by using a sulfurizing reagent. Nevertheless, the main drawbacks remain the difficulties in adjusting the degree of thionation and obtaining tri- and tetrathionated PDIs. Up to now, this thionation reaction has been described almost exclusively using Lawesson’s reagent. In the current study, we present our first investigations into an alternative reagent to enhance selectivity and achieve a greater degree of thionation. The association of phosphorus pentasulfide with hexamethyldisiloxane (Curphey’s reagent) clearly demonstrated higher reactivity compared with Lawesson’s reagent to attain multi-thionated PDIs. Full article

(This article belongs to the Special Issue Organosulfur and Organoselenium Chemistry)

► Show Figures

Figure 1

28 pages, 11924 KiB

Open AccessReview

Towards More Practical Methods for the Chemical Synthesis of Thioamides Using Sulfuration Agents: A Decade Update

by Qiang Zhang, Laurent Soulère and Yves Queneau

Molecules 2023, 28(8), 3527; https://doi.org/10.3390/molecules28083527 - 17 Apr 2023

Cited by 7 | Viewed by 2660

Abstract

Compounds possessing a thioamide function play a crucial role in organic synthesis, serving as key building blocks. They are also important in the pharmaceutical chemistry and drug design, owing to their ability to mimic the amide function in biomolecules while retaining or developing [...] Read more.

Compounds possessing a thioamide function play a crucial role in organic synthesis, serving as key building blocks. They are also important in the pharmaceutical chemistry and drug design, owing to their ability to mimic the amide function in biomolecules while retaining or developing biological activity. From the synthetic viewpoint, several methods have been developed for preparing thioamides using sulfuration agents. The purpose of this review is to give an update of the last decade of contributions focusing on the formation of thioamides employing different sulfur sources. When appropriate, the cleanness and practicality of the new methods are highlighted. Full article

(This article belongs to the Special Issue Organosulfur and Organoselenium Chemistry)

► Show Figures

Figure 1

Journal Menu

Journal Browser

Organosulfur and Organoselenium Chemistry

Share This Special Issue

Special Issue Editor

Special Issue Information

Keywords

Benefits of Publishing in a Special Issue

Published Papers (9 papers)

Research

Review

Further Information

Guidelines

MDPI Initiatives

Follow MDPI