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In this review, we discuss all sulfur-containing FDA-approved drugs and their structures. The second section of the review is dedicated to structural analysis and is divided into 14 subsections, each focusing on one type of sulfur-containing moiety. A concise graphical representation of each class features drugs that are organized on the basis of s...
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... Notwithstanding this recent progress, there are still significant limitations in the scope of available reactions suitable for light alkane activation. Sulfones, sulfonamides, and sulfonate esters represent ubiquitous functional groups with applications spanning various fields, including pharmaceuticals 17,18 , agrochemicals 19,20 , and material science (Fig. 1C) 21 . Commonly, sulfinate salts serve as versatile precursors for constructing sulfur-containing compounds due to their reactivity and stability 22,23 . ...
Sulfur-containing scaffolds originating from small alkyl fragments play a crucial role in various pharmaceuticals, agrochemicals, and materials. Nonetheless, their synthesis using conventional methods presents significant challenges. In this study, we introduce a practical and efficient approach that harnesses hydrogen atom transfer photocatalysis to activate volatile alkanes, such as isobutane, butane, propane, ethane, and methane. Subsequently, these nucleophilic radicals react with SO2 to yield the corresponding sulfinates. These sulfinates then serve as versatile building blocks for the synthesis of diverse sulfur-containing organic compounds, including sulfones, sulfonamides, and sulfonate esters. Our use of flow technology offers a robust, safe and scalable platform for effectively activating these challenging gaseous alkanes, facilitating their transformation into valuable sulfinates.
... Despite some impressive advances have been achieved, the breadth and depth of chiral skeletal diversification in discovery and development of new drugs are still constrained due to the unsolved problems in particularly important catalytic asymmetric transformations 4 . In this scenario, a conspicuous example is that the sporadic occurrence of catalytic protocols towards chiral sulfinamides, a class of stereogenic-at-S(IV) scaffolds, which is thus difficult to fulfill the demands of systematically biological screening (Fig. 1a) [5][6][7][8][9][10][11][12][13][14] . To date, the most conventional and widely employed approach for synthesizing chiral sulfinamides primarily relies on using chiral starting materials [15][16][17] or employing stoichiometric amounts of chiral auxiliaries 18,19 . ...
The enantioselective synthesis of S-stereogenic sulfinamides has garnered considerable attention due to their structural and physicochemical properties. However, catalytic asymmetric synthesis of sulfinamides still remains daunting challenges, impeding their broad application in drug discovery and development. Here, we present an approach for the synthesis of S-stereogenic sulfinamides through peptide-mimic phosphonium salt-catalyzed asymmetric skeletal reorganization of simple prochiral and/or racemic sulfoximines. This methodology allows for the facile access to a diverse array of substituted sulfinamides with excellent enantioselectivities, accommodating various substituent patterns through desymmetrization or parallel kinetic resolution process. Mechanistic experiments, coupled with density functional theory calculations, clarify a stepwise pathway involving ring-opening and ring-closing processes, with the ring-opening step identified as crucial for achieving stereoselective control. Given the prevalence of S-stereogenic centers in pharmaceuticals, we anticipate that this protocol will enhance the efficient and precise synthesis of relevant chiral molecules and their analogs, thereby contributing to advancements in drug discovery.
... Cyclic sulfoxides and sulfones are important pharmacophores with a wide range of pharmacological activities due to their various mechanisms of action. 61,62 ■ RESULTS AND DISCUSSION Initially, using a metal-free nucleophilic aromatic substitution (S N Ar) reaction 58,60,63−66 and a Grignard reaction, we synthesized starting chemicals in two steps (Scheme 1). ...
In this study, a series of halogen-substituted thioxanthenes were synthesized because the most important and biologically active derivatives of xanthenes are thioxanthenes. In order to obtain new thioxanthene derivatives, first, the starting molecules were synthesized by the appropriate reaction methods in two steps. The intramolecular Friedel–Crafts alkylation (FCA) method was used to convert the prepared three aromatic substituted starting alcohol compounds to their corresponding thioxanthenes by cyclization. For the intramolecular FCA reaction of secondary alcohols, which are the starting compounds (1a–1t), organic Bro̷nsted acids, which require more innovative, easier, and suitable reaction conditions, were used instead of halide reagents with corrosive effects as classical FCA catalysts. Trifluoroacetic acid was determined to be the organocatalyst with the best yield. Therefore, some original 9-aryl/alkyl thioxanthene derivatives (2a–2t) were synthesized using the optimized FCA method. In addition, a new sulfone derivative of thioxanthene 3i was prepared by performing the oxidation reaction with one of the obtained new thioxanthene 2i. Thioxanthenes and their derivatives are important heterocyclic structures that contain pharmacologically valuable sulfur and are used in the treatment of psychotic diseases such as Alzheimer’s or schizophrenia, as well as a number of potent biological activities.
... Organic sulfur compounds constitute one of the most important classes of organic compounds which have found wide application in various fields of human activity [1][2][3][4][5][6][7][8][9]. Among them, of particular interest are sulfonyl-containing compounds (sulfones), including β-halovinyl sulfones and their derivatives obtained by the substitution of halogen by other functional groups [10][11][12][13][14][15][16]. ...
A number of β-iodovinyl sulfones were synthesized by direct difunctionalization of internal alkynes with arenesulfonyl iodides under irradiation with red light (λ max 625 nm) generated by an economical LED source. The products were obtained in high yields (68–99%) from equimolar amounts of the reactants. The reaction of sulfonyl iodides with internal alkynes follows a radical mechanism and provides a regioselective method of synthesis of β-iodovinyl sulfones.
... Synthesis of the biologically active compounds is very important [1][2][3][4][5][6][7][8][9][10][11][12]. Thioesters (thiocarboxylates) are one of the most important classes of organosulfur compounds found in numerous natural products [13], pharmaceutical [14] and agricultural chemicals [15]. In addition, they represent excellent building blocks to synthesize various organic functional materials such as ketones [16], aldehydes [17], esters [18], and amides [19], acylsilanes [20], dithioesters [21], 2-methylthio-1, 3-oxazoles [22], and many more [23,24]. ...
Thioesters are a class of highly useful compounds in synthetic chemistry,
and many thioester compounds show biological and pharmacological
activities. Organic halides and thiols are widely accessible chemical
feedstocks and are widely used in industry as building blocks. The synthesis
of thioesters from these basic chemicals is important for chemical synthesis
nowadays. Over the years, many efforts have been made to access thioester
derivatives through thiocarbonylation of organic halides with thiols using
different carbon monoxide sources including CO, CO2, COgen,
[CpFe(CO)2]2, Cr(CO)6, etc. Herein, we summarize the recent advances of
these carbonylative coupling reactions.
... Mechanistic results support a biomimetic radical homolytic substitution pathway for the critical C(sp 3 )-S bond formation step. α-Chiral alkyl thiols and other organosulfur moieties with different sulfur oxidation states are important chiral building blocks in organic synthesis 1,2 and biochemical processes 3 , and are also key structural elements in a variety of biomolecules, pharmaceuticals and agrochemicals [3][4][5][6] . For example, they are widely present in many chiral organocatalysts 7,8 and ligands 9,10 for diverse asymmetric transformations. ...
Although α-chiral C(sp³)–S bonds are of enormous importance in organic synthesis and related areas, the transition-metal-catalysed enantioselective C(sp³)–S bond construction still represents an underdeveloped domain probably due to the difficult heterolytic metal–sulfur bond cleavage and notorious catalyst-poisoning capability of sulfur nucleophiles. Here we demonstrate the use of chiral tridentate anionic ligands in combination with Cu(I) catalysts to enable a biomimetic enantioconvergent radical C(sp³)–S cross-coupling reaction of both racemic secondary and tertiary alkyl halides with highly transformable sulfur nucleophiles. This protocol not only exhibits a broad substrate scope with high enantioselectivity but also provides universal access to a range of useful α-chiral alkyl organosulfur compounds with different sulfur oxidation states, thus providing a complementary approach to known asymmetric C(sp³)–S bond formation methods. Mechanistic results support a biomimetic radical homolytic substitution pathway for the critical C(sp³)–S bond formation step.
... In this context, numerous methodologies have been reported for their synthesis [10]. On the other hand, as a prominent class of organosulfur compounds, sulfones play a pivotal role in various drugs, pesticides and natural products [11][12][13][14][15][16][17]. To date, methods for the construction of sulfonyl compounds from sulfonyl chlorides, sodium sulfinates or sulfur dioxide surrogates have attracted considerable attention, and significant progress has been made in this area [18][19][20][21][22][23][24]. ...
... CO 3 ) produced inferior results(Table 1, entries 8-10). Finally, the effect of solvent was examined, and the reaction in THF and CH 3 CN resulted in moderate yields(Table 1, entries[11][12]. Optimization of the reaction conditions a . ...
Both sulfonyl and phosphorothioate are important privileged structural motifs which are widely presented in pharmaceuticals and agrochemicals. Herein, we describe an efficient approach to synthesizing sulfonyl-containing phosphorothioates by merging photoredox and copper catalysis at room temperature. This protocol is compatible with a wide range of substrates and can be applied to the late-stage modification of complex molecules. Control experiments are conducted to demonstrate the generation of the sulfonyl radical in the transformation.
... Similarly, the distinctive and versatile sulfur-containing drugs enable sulfonamides or sulfonyls to occupy a significant stance in the medicinal world [47][48][49][50][51], facilitating their integration as an additional pharmacophore in constructing a synthetically enhanced molecular scaffold. Since the discovery of the first successful antimicrobial sulfonamide drug Prontosil rubrum, around 100 FDA-established potential sulfonamide drugs are available in the market [52] that have a huge range of therapeutic antibiotic and anticancer applications [53][54][55][56][57][58][59][60][61][62][63]. Evidently, the FDA has granted clearance to several sulfonamide molecules in tumor treatment. ...
In this study, novel selective antitumor compounds were synthesized based on their fundamental pharmacophoric prerequisites associated with EGFR inhibitors. A molecular hybridization approach was employed to design and prepare a range of 4H-chromene-3-carboxylates 7a–g, 8, and 11a–e derivatives, each incorporating a sulfonamide moiety. The structures of these hybrid molecules were verified using comprehensive analytical and spectroscopic techniques. During the assessment of the newly synthesized compounds for their anticancer properties against three tumor cell lines (HepG-2, MCF-7, and HCT-116), compounds 7f and 7g displayed remarkable antitumor activity against all tested cell lines, outperforming the reference drug Cisplatin in terms of efficacy. Consequently, these promising candidates were selected for further investigation of their anti-EGFR, hCAII, and MMP-2 potential, which exhibited remarkable effectiveness against EGFR and MMP2 when compared to Sorafenib. Additionally, docking investigations regarding the EGFR binding site were implemented for the targeted derivatives in order to attain better comprehension with respect to the pattern in which binding mechanics occur between the investigated molecules and the active site, which illustrated a higher binding efficacy in comparison with Sorafenib.
... On the one hand, heterocycles are widely present in many agrochemical and pharmaceutical products [22][23][24][25][26][27][28]. To date, the number of pharmaceutical products containing a heterocyclic part in their skeleton, and in particular bicyclic heterocycles, is estimated to be around 70%, hence the importance of mastering synthesis protocols and carrying them out under the safest possible conditions, for the development and production of new environmentally friendly drugs or agrochemical compounds [25,[29][30][31]. ...
Following the work already carried out in our laboratory on eucalyptol, a new green solvent derived from biomass, we are now looking at sabinene as another new green solvent. Sabinene is also derived from biomass, has no known toxicity and can be recycled by distillation. We have shown that it can be used as it is or distilled to synthesize thiazolo[5,4-b]pyridine heterocycles by thermal activation or microwave irradiation. This new solvent was compared with various conventional and green solvents. The conditions were optimised to enable us to carry out the syntheses in satisfactory yields, and we were able to show that sabinene, a natural bicyclic monoterpene, could be used effectively as a solvent.
... Catalysts 2023, 13, 1300 2 of 36 are known by their antioxidant [17,18], antitumoral [19][20][21], antimicrobial [22,23], and anti-inflammatory activities [24]. Several are heterocyclic systems containing sulfur on its structure available as FDA-approved drugs [25,26]. On the other hand, organoselenium and organotellurium derivatives display unique reactivity profiles, making them valuable as catalysts, ligands, and intermediates in synthetic methodologies [27][28][29]. ...
... From the viewpoint of biological activities, organochalcogen compounds are known by their antioxidant [17,18], antitumoral [19][20][21], antimicrobial [22,23], and anti-inflammatory activities [24]. Several are heterocyclic systems containing sulfur on its structure available as FDA-approved drugs [25,26]. On the other hand, organoselenium and organotellurium derivatives display unique reactivity profiles, making them valuable as catalysts, ligands, and intermediates in synthetic methodologies [27][28][29]. ...
Organochalcogen-bearing heterocycles are important scaffolds in compounds under the spotlight of scientific interest in optoelectronic fields and for biological applications. The use of transition metals has been a versatile and reliable way to carry out the synthesis of these molecules efficiently, delivering products in high yields and with a wide functional diversity. In the last 10 years, many classes of heterocycles have been synthesized under the cyclization reaction of acyclic alkenes and alkynes with the incorporation of a chalcogen atom on its structure. Transition metal catalysts including Cu, Co, Pd, Ni, In, Ag, and Fe salts have been used in the development of new methodologies, the expansion of substrate scope, and mechanistic studies. This review provides an overview of these recent approaches with the aim of being a useful resource for interested researchers in this area.
