Since the early 2000s, novel synthetic methods for the preparation of sulfoxides have emerged that involve sulfenate anions as sulfur nucleophiles. This short review showcases key advances in these sulfenate protocols, including catalytic enantioselective alkylation and arylation, and provides future directions for this research field.
{"title":"Recent Developments on the Synthesis of Sulfoxides via Sulfenate Anions","authors":"Fumito Saito","doi":"10.1055/a-2155-3498","DOIUrl":"https://doi.org/10.1055/a-2155-3498","url":null,"abstract":"Since the early 2000s, novel synthetic methods for the preparation of sulfoxides have emerged that involve sulfenate anions as sulfur nucleophiles. This short review showcases key advances in these sulfenate protocols, including catalytic enantioselective alkylation and arylation, and provides future directions for this research field.","PeriodicalId":49451,"journal":{"name":"Synthesis-Stuttgart","volume":"10 1","pages":""},"PeriodicalIF":2.6,"publicationDate":"2023-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87435116","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
using thioanisole and p -toluenesulfonamide as test substrates. Indeed, selective formation of the sulfilimine was observed when bromide was used as the mediator and MeOH as the base. In addition, bromide and MeOH also served as supporting electrolyte and solvent, which allowed for an extremely efficient use of the reactants.
{"title":"SYNFORM ISSUE 2023/8","authors":"M. Zanda","doi":"10.1055/s-0040-1720605","DOIUrl":"https://doi.org/10.1055/s-0040-1720605","url":null,"abstract":"using thioanisole and p -toluenesulfonamide as test substrates. Indeed, selective formation of the sulfilimine was observed when bromide was used as the mediator and MeOH as the base. In addition, bromide and MeOH also served as supporting electrolyte and solvent, which allowed for an extremely efficient use of the reactants.","PeriodicalId":49451,"journal":{"name":"Synthesis-Stuttgart","volume":"4 1","pages":"A133 - A148"},"PeriodicalIF":2.6,"publicationDate":"2023-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84443103","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ulises Jose Vargas-Cruz, José G. Peralta-Chávez, Misael A. Romero-Reyes, D. Martínez-Otero, M. Romero-Ortega
An aromatic C–H nitrene insertion of 2-trichloromethylpyrimidines bearing a phenyl substituent in C-5 position is described. Treatment of 2-trichloromethyl-4-chloro-5-phenylpyrimidines with sodium azide in DMF or the reflux of 2-trichloromethyl-4-azido-5-phenylpyrimidines in toluene provided 2-trichloromethylpyrimido[4,5-b]indole derivatives in moderate yields. Excellent yields of this heterocyclic systems were obtained through of the aromatic C–H insertion with Du Bois catalyst. This is an attractive approach for synthesizing pyrimido[4,5-b]indoles with a trichloromethyl substituent in the pyrimidine moiety.
{"title":"Nitrene Cyclization of 2-(Trichloromethyl)-5-phenylpyrimidines: Application to the Synthesis of 2-(Trichloromethyl)pyrimido[4,5- b ]indoles and Related Heterocycles","authors":"Ulises Jose Vargas-Cruz, José G. Peralta-Chávez, Misael A. Romero-Reyes, D. Martínez-Otero, M. Romero-Ortega","doi":"10.1055/a-2159-1611","DOIUrl":"https://doi.org/10.1055/a-2159-1611","url":null,"abstract":"An aromatic C–H nitrene insertion of 2-trichloromethylpyrimidines bearing a phenyl substituent in C-5 position is described. Treatment of 2-trichloromethyl-4-chloro-5-phenylpyrimidines with sodium azide in DMF or the reflux of 2-trichloromethyl-4-azido-5-phenylpyrimidines in toluene provided 2-trichloromethylpyrimido[4,5-b]indole derivatives in moderate yields. Excellent yields of this heterocyclic systems were obtained through of the aromatic C–H insertion with Du Bois catalyst. This is an attractive approach for synthesizing pyrimido[4,5-b]indoles with a trichloromethyl substituent in the pyrimidine moiety.","PeriodicalId":49451,"journal":{"name":"Synthesis-Stuttgart","volume":"72 1","pages":""},"PeriodicalIF":2.6,"publicationDate":"2023-07-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84105050","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Daniel Jahani, H. Yassine, Mostafa Khouili, M. D. Pujol
ABSTRACT: The first method for the direct conversion of carboxylic acids into ureas has been developed. The classical procedures described above for the formation of ureas from carboxylic acids require two steps, preparation of the isocyanate followed by its aminolysis. In this work, arylcarboxylic and arylalkylcarboxylic acids have been transformed into symmetric ureas in a single step using DPPA or sodium azide as nitrogen source. The addition of water (method A) or the presence of solvent water (method B) was essential for the formation of symmetrical ureas from the corresponding carboxylic acids. The corresponding ureas have been obtained in good to excellent yields of 46 to 100%. This procedure was compatible with differ-ent substituents present in the starting carboxylic acid.
{"title":"New Route to Direct Synthesis of Symmetrical Ureas from Carboxylic Acids","authors":"Daniel Jahani, H. Yassine, Mostafa Khouili, M. D. Pujol","doi":"10.1055/a-2172-8329","DOIUrl":"https://doi.org/10.1055/a-2172-8329","url":null,"abstract":"ABSTRACT: The first method for the direct conversion of carboxylic acids into ureas has been developed. The classical procedures described above for the formation of ureas from carboxylic acids require two steps, preparation of the isocyanate followed by its aminolysis. In this work, arylcarboxylic and arylalkylcarboxylic acids have been transformed into symmetric ureas in a single step using DPPA or sodium azide as nitrogen source. The addition of water (method A) or the presence of solvent water (method B) was essential for the formation of symmetrical ureas from the corresponding carboxylic acids. The corresponding ureas have been obtained in good to excellent yields of 46 to 100%. This procedure was compatible with differ-ent substituents present in the starting carboxylic acid.","PeriodicalId":49451,"journal":{"name":"Synthesis-Stuttgart","volume":"68 6 1","pages":""},"PeriodicalIF":2.6,"publicationDate":"2023-07-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76495965","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
C-H deprotometalations have long occupied a key role in modern organic synthesis in both the research laboratory and pharmaceutical and fine chemical manufacture, thanks to readily accessible reagents and well-established procedures. Typically, organolithiums are the reagent of choice thanks to high reactivity and ease of use but these are incompatible with base- and nucleophile-sensitive functional groups. In comparison, organozinc base complexes offer a milder approach to deprotonative C-H functionalisations, and compatibility with a wide range of functionalities which would be problematic when using the alternative organolithium or organomagnesium reagents has now been demonstrated. Here, we review the current state of the art in zinc-mediated C-H metalations at substituted arenes, heteroarenes and Csp3-H sites.
{"title":"Zinc-Mediated C–H Metalations in Modern Organic Synthesis","authors":"Daria Karolina Wanic, Rebecca Melvin, G. Barker","doi":"10.1055/a-2155-3423","DOIUrl":"https://doi.org/10.1055/a-2155-3423","url":null,"abstract":"C-H deprotometalations have long occupied a key role in modern organic synthesis in both the research laboratory and pharmaceutical and fine chemical manufacture, thanks to readily accessible reagents and well-established procedures. Typically, organolithiums are the reagent of choice thanks to high reactivity and ease of use but these are incompatible with base- and nucleophile-sensitive functional groups. In comparison, organozinc base complexes offer a milder approach to deprotonative C-H functionalisations, and compatibility with a wide range of functionalities which would be problematic when using the alternative organolithium or organomagnesium reagents has now been demonstrated. Here, we review the current state of the art in zinc-mediated C-H metalations at substituted arenes, heteroarenes and Csp3-H sites.","PeriodicalId":49451,"journal":{"name":"Synthesis-Stuttgart","volume":"18 1","pages":"3487 - 3501"},"PeriodicalIF":2.6,"publicationDate":"2023-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82193134","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A visible-light-mediated metal-free oxidation of 1-BnDHIQs to switchable preparation of BzIQs and BzDHIQs has been realized in which dioxygen as an oxidant. 6,7-Dialkoxy BzIQs and BzDHIQs were comprehensively synthesized in this protocol. This protocol provides a facile route for the efficient synthesis of isoquinoline alkaloids. Mechanistic investigation suggested that radical pathway and ionic pathway may exist simultaneously and intermediate A may be the key compound for the formation of the products.
{"title":"Visible-Light-Mediated Oxidation of 1-Benzyl-3,4-dihydroisoquinolines with Dioxygen: A Switchable Synthesis of 1-Benzoylisoquinolines and 1-Benzoyl-3,4-dihydroisoquinolines","authors":"Peipei Ma, Hongli Wu, H. Gan","doi":"10.1055/a-2160-8903","DOIUrl":"https://doi.org/10.1055/a-2160-8903","url":null,"abstract":"A visible-light-mediated metal-free oxidation of 1-BnDHIQs to switchable preparation of BzIQs and BzDHIQs has been realized in which dioxygen as an oxidant. 6,7-Dialkoxy BzIQs and BzDHIQs were comprehensively synthesized in this protocol. This protocol provides a facile route for the efficient synthesis of isoquinoline alkaloids. Mechanistic investigation suggested that radical pathway and ionic pathway may exist simultaneously and intermediate A may be the key compound for the formation of the products.","PeriodicalId":49451,"journal":{"name":"Synthesis-Stuttgart","volume":"1 1","pages":""},"PeriodicalIF":2.6,"publicationDate":"2023-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76957653","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The fluorine-directing effect has so far been exploited to provide short and efficient synthetic routes to rare L-ido sugars. However, the importance of anomeric configuration to its success has remained experimentally unverified. We now report on the synthesis of α- and β-configured per-O-benzoylated mannopyranosyl fluorides and initially show that their reactivity towards photo-bromination is strongly dependent on the anomeric configuration. The stereochemical basis of the fluorine-directing effect is then validated by revealing the striking difference in stereoselectivity observed for the free radical reductions of the isolated 5-C-bromo sugars. This work importantly provides a synthetic route to a donor-functionalised derivative of L-gulose and reveals new insights into the behaviour of glycosyl radicals.
迄今为止，利用氟定向效应为稀有的L-ido糖提供了短而有效的合成途径。然而，对其成功的重要性的异构体结构仍未得到实验证实。我们现在报道了α-和β-构型的对o-苯甲酰化甘露吡喃基氟化物的合成，并初步表明它们对光溴化的反应性强烈依赖于端粒构型。然后，通过揭示分离的5- c -溴糖的自由基还原所观察到的立体选择性的显著差异，验证了氟定向效应的立体化学基础。这项工作为l -葡糖的供体功能化衍生物提供了一条重要的合成途径，并揭示了对糖基自由基行为的新见解。
{"title":"C-5 Epimerisation of d -Mannopyranosyl Fluorides: The Influence of Anomeric Configuration on Radical Reactivity","authors":"Nicholas W. See, G. Pierens, E. Krenske, V. Ferro","doi":"10.1055/a-2149-4586","DOIUrl":"https://doi.org/10.1055/a-2149-4586","url":null,"abstract":"The fluorine-directing effect has so far been exploited to provide short and efficient synthetic routes to rare L-ido sugars. However, the importance of anomeric configuration to its success has remained experimentally unverified. We now report on the synthesis of α- and β-configured per-O-benzoylated mannopyranosyl fluorides and initially show that their reactivity towards photo-bromination is strongly dependent on the anomeric configuration. The stereochemical basis of the fluorine-directing effect is then validated by revealing the striking difference in stereoselectivity observed for the free radical reductions of the isolated 5-C-bromo sugars. This work importantly provides a synthetic route to a donor-functionalised derivative of L-gulose and reveals new insights into the behaviour of glycosyl radicals.","PeriodicalId":49451,"journal":{"name":"Synthesis-Stuttgart","volume":"31 1","pages":""},"PeriodicalIF":2.6,"publicationDate":"2023-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82424639","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
An efficient access to enantioenriched cyclic homopropargylic alcohols through an unprecedented cobalt-catalyzed asymmetric alkynylation of oxabicyclic alkenes. By using inexpensive cobalt salt/chiral bisphosphine ligand as the catalyst and easy-to-handle potassium alkynyltrifluoroborates as the nucleophiles, synthetically valuable homopropargylic alcohols are obtained in moderate to good yields and high enantioselectivities.
{"title":"Cobalt-Catalyzed Enantioselective Alkynylation of Oxabicyclic Alkenes","authors":"Lin-Wen Wei, Zhan-Cai Ma, Zhao Wang, Yu Zhao, Yuan Huang","doi":"10.1055/a-2152-0355","DOIUrl":"https://doi.org/10.1055/a-2152-0355","url":null,"abstract":"An efficient access to enantioenriched cyclic homopropargylic alcohols through an unprecedented cobalt-catalyzed asymmetric alkynylation of oxabicyclic alkenes. By using inexpensive cobalt salt/chiral bisphosphine ligand as the catalyst and easy-to-handle potassium alkynyltrifluoroborates as the nucleophiles, synthetically valuable homopropargylic alcohols are obtained in moderate to good yields and high enantioselectivities.","PeriodicalId":49451,"journal":{"name":"Synthesis-Stuttgart","volume":"16 1","pages":""},"PeriodicalIF":2.6,"publicationDate":"2023-07-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"81466542","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sumit Kumar Singh, Sunil Kumar, Mangal S Yadav, S. Bhattacharya, V. Tiwari
The report describes a convenient method for the Cu(I)-catalyzed tandem synthesis of dihydrophenanthridine-diones and substituted isoquinolinones with the assistance of efficient glycosyl 1,2,3-triazole-based pyridinamide ligands. The catalytic system effectively works for the coupling of N-substituted 2-halobenzamides with various active methylene compounds to achieve a high-to-excellent yield of biologically relevant heterocyclic scaffolds. The consecutive path of the reaction including intermolecular C-C cross-coupling followed by intramolecular cyclization efficiently takes place at low catalytic loading. These glycosyl triazole-appended pyridinamides were synthesized in good yields via CuI/DIPEA mediated regioselective CuAAC click tool. There are some notable features of the method, including low catalytic loading, the cost-effective and biocompatible nature of ligands, high reaction yield, and easily accessible starting materials that make the protocol more versatile.
{"title":"Glycosyl Triazole Based Pyridinamide/CuI-Catalyzed Coupling of 2-Halobenzamides with Active Methylene Compounds","authors":"Sumit Kumar Singh, Sunil Kumar, Mangal S Yadav, S. Bhattacharya, V. Tiwari","doi":"10.1055/a-2157-9001","DOIUrl":"https://doi.org/10.1055/a-2157-9001","url":null,"abstract":"The report describes a convenient method for the Cu(I)-catalyzed tandem synthesis of dihydrophenanthridine-diones and substituted isoquinolinones with the assistance of efficient glycosyl 1,2,3-triazole-based pyridinamide ligands. The catalytic system effectively works for the coupling of N-substituted 2-halobenzamides with various active methylene compounds to achieve a high-to-excellent yield of biologically relevant heterocyclic scaffolds. The consecutive path of the reaction including intermolecular C-C cross-coupling followed by intramolecular cyclization efficiently takes place at low catalytic loading. These glycosyl triazole-appended pyridinamides were synthesized in good yields via CuI/DIPEA mediated regioselective CuAAC click tool. There are some notable features of the method, including low catalytic loading, the cost-effective and biocompatible nature of ligands, high reaction yield, and easily accessible starting materials that make the protocol more versatile.","PeriodicalId":49451,"journal":{"name":"Synthesis-Stuttgart","volume":"98 9 1","pages":""},"PeriodicalIF":2.6,"publicationDate":"2023-07-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83324781","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Narayanasamy Nivetha, Shashank M. Patil, R. Ramu, S. Sreenivasa, S. Velmathi
A higly functionalized spirooxindole pyrrolizidine/pyrrolothiazole derivatives has been synthesised by the three-component 1,3-dipolar cycloaddition reaction of benzothiazolyl amides with isatin-based azomethine ylides. The pharmacologically significant spirooxindole derivatives bearing one quaternary carbon and four stereocentres were obtained in excellent yields (up to 93 %). The compounds were screened for their anti-diabetic activity against two enzymes, α-glucosidase and α-amylase. The results exhibited potent inhibitory activity against these enzymes, especially compound 6b, which showed excellent activity compared to the standard acarbose. Molecular docking against the receptors showed excellent interactions of the synthesized compounds in a similar way to acarbose. Further, the docking results of compound 6b evinced the strong binding interactions of the compound with the receptors. Additionally, molecular dynamics simulations were carried out and confirmed the stability of compound 6b in the active pockets of enzymes over 100 ns.
{"title":"Stereoselective Synthesis of Highly Functionalized Aminobenzothiazole-Fused Spirooxindole Derivatives: in silico and in vitro Anti-Diabetic Studies","authors":"Narayanasamy Nivetha, Shashank M. Patil, R. Ramu, S. Sreenivasa, S. Velmathi","doi":"10.1055/a-2161-0283","DOIUrl":"https://doi.org/10.1055/a-2161-0283","url":null,"abstract":"A higly functionalized spirooxindole pyrrolizidine/pyrrolothiazole derivatives has been synthesised by the three-component 1,3-dipolar cycloaddition reaction of benzothiazolyl amides with isatin-based azomethine ylides. The pharmacologically significant spirooxindole derivatives bearing one quaternary carbon and four stereocentres were obtained in excellent yields (up to 93 %). The compounds were screened for their anti-diabetic activity against two enzymes, α-glucosidase and α-amylase. The results exhibited potent inhibitory activity against these enzymes, especially compound 6b, which showed excellent activity compared to the standard acarbose. Molecular docking against the receptors showed excellent interactions of the synthesized compounds in a similar way to acarbose. Further, the docking results of compound 6b evinced the strong binding interactions of the compound with the receptors. Additionally, molecular dynamics simulations were carried out and confirmed the stability of compound 6b in the active pockets of enzymes over 100 ns.","PeriodicalId":49451,"journal":{"name":"Synthesis-Stuttgart","volume":"205 1","pages":""},"PeriodicalIF":2.6,"publicationDate":"2023-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84234266","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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