This review provides a comprehensive overview of asymmetric Negishi and Kumada crosscoupling reactions, covering key developments from the 1980s through 2025. It examines enantioselective and enantiospecific variants catalyzed by nickel, palladium, and cobalt complexes. The review discusses reaction scope, mechanistic ligand design and mechanistic understanding have enabled increasingly challenging transformations with high enantioselectivity Overall, this review demonstrates the power and versatility of asymmetric Negishi and Kumada couplings as valuable tools for constructing chiral molecules.
{"title":"Asymmetric Negishi and Kumada Couplings","authors":"Rui-Heng Wang, Aishun Ding, Ramon Rios","doi":"10.1002/adsc.70204","DOIUrl":"https://doi.org/10.1002/adsc.70204","url":null,"abstract":"This review provides a comprehensive overview of asymmetric Negishi and Kumada crosscoupling reactions, covering key developments from the 1980s through 2025. It examines enantioselective and enantiospecific variants catalyzed by nickel, palladium, and cobalt complexes. The review discusses reaction scope, mechanistic ligand design and mechanistic understanding have enabled increasingly challenging transformations with high enantioselectivity Overall, this review demonstrates the power and versatility of asymmetric Negishi and Kumada couplings as valuable tools for constructing chiral molecules.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"8 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146205569","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In this study, we have synthesized a series of neutral and cationic silver complexes bearing two different redox-active N-heterocyclic carbene (NHC) ligands. Neutral complexes of the type Nq(IDipp)AgOCOR (R = CH3 (2b), Ph (2c), CF3 (2d)) were obtained via the reaction of imidazolium salts or the corresponding free carbenes with silver precursors. In contrast, cationic complexes of the general formula [Nq(NHC)2Ag)]X (NHC = IDipp, X = BF4 (3a), SbF6 (3b); NHC = IMes, X = BF4 (3c), SbF6 (3d)) were prepared using AgX salts. The complex Nq(IDipp)AgOCOCH3 (2b) was used as a catalyst for the carboxylative cyclization of substituted propargyl amines with CO2 gas and outperforms the nonredox active NHC-silver complexes. This transformation enabled the development of a new and efficient catalytic protocol for the synthesis of a broad range of oxazolidine-2-ones in good to excellent yields. Notably, catalyst 2b exhibited excellent catalytic performance under mild conditions, operating effectively at low CO2 gas concentrations and in the absence of bases or additives.
{"title":"Redox-Active N-Heterocyclic Carbene-Bearing Silver(I) Complexes: Synthesis and Novel Catalysts for CO2 Utilization in the Carboxylative Cyclization of Propargyl Amines","authors":"Aiswarya Moharana, Jyotikiran Sahoo, Suraj Kumar Agrawalla, Chandra Shekhar Purohit, Adinarayana Doddi","doi":"10.1002/adsc.70308","DOIUrl":"https://doi.org/10.1002/adsc.70308","url":null,"abstract":"In this study, we have synthesized a series of neutral and cationic silver complexes bearing two different redox-active N-heterocyclic carbene (NHC) ligands. Neutral complexes of the type Nq(IDipp)AgOCOR (R = CH<sub>3</sub> (<b>2b</b>), Ph (<b>2c</b>), CF<sub>3</sub> (<b>2d</b>)) were obtained via the reaction of imidazolium salts or the corresponding free carbenes with silver precursors. In contrast, cationic complexes of the general formula [Nq(NHC)<sub>2</sub>Ag)]X (NHC = IDipp, X = BF<sub>4</sub> (<b>3a</b>), SbF<sub>6</sub> (<b>3b</b>); NHC = IMes, X = BF<sub>4</sub> (<b>3c</b>), SbF<sub>6</sub> (<b>3d</b>)) were prepared using AgX salts. The complex Nq(IDipp)AgOCOCH<sub>3</sub> (<b>2b</b>) was used as a catalyst for the carboxylative cyclization of substituted propargyl amines with CO<sub>2</sub> gas and outperforms the nonredox active NHC-silver complexes. This transformation enabled the development of a new and efficient catalytic protocol for the synthesis of a broad range of oxazolidine-2-ones in good to excellent yields. Notably, catalyst <b>2b</b> exhibited excellent catalytic performance under mild conditions, operating effectively at low CO<sub>2</sub> gas concentrations and in the absence of bases or additives.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"23 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146205570","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Lu‐Yao Wang, Ting Liu, Wei‐Zhen Wang, Xinglei He, Ke‐Yin Ye
An electrochemical migratory cyclization of N ‐acylsulfonylimine readily generates the biologically interesting sulfonylimine‐functionalized benzothiazine. The implementation of continuous flow electrolysis further enhances reaction efficiency and enables gram‐scale synthesis of this heterocyclic framework, providing the material basis for future biological activity studies. In addition, a straightforward electrochemical entry to the previously inaccessible benzothiazepine from N ‐arylsulfonyl benzothioamide is developed.
N -酰基磺酰亚胺的电化学迁移环化很容易产生具有生物学意义的磺酰亚胺功能化苯并噻嗪。连续流电解的实施进一步提高了反应效率，使该杂环骨架的克级合成成为可能，为未来的生物活性研究提供了物质基础。此外，还开发了一种从N -芳基磺酰基苯并噻唑酰胺中直接进入苯并噻唑的电化学方法。
{"title":"Electrochemical Migratory Cyclization of N ‐Acylsulfonimide and N ‐Arylsulfonyl Benzothiamide","authors":"Lu‐Yao Wang, Ting Liu, Wei‐Zhen Wang, Xinglei He, Ke‐Yin Ye","doi":"10.1002/adsc.70292","DOIUrl":"https://doi.org/10.1002/adsc.70292","url":null,"abstract":"An electrochemical migratory cyclization of <jats:italic>N</jats:italic> ‐acylsulfonylimine readily generates the biologically interesting sulfonylimine‐functionalized benzothiazine. The implementation of continuous flow electrolysis further enhances reaction efficiency and enables gram‐scale synthesis of this heterocyclic framework, providing the material basis for future biological activity studies. In addition, a straightforward electrochemical entry to the previously inaccessible benzothiazepine from <jats:italic>N</jats:italic> ‐arylsulfonyl benzothioamide is developed.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"36 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146198900","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Rodrigo G. Enríquez, Juan S. Dato‐Santiago, Aitor Rivas‐Cobollo, José Alemán, Jose A. Fernández‐Salas
In this work, we describe how N‐hydroxyphthalimide (NHPI), also under catalytic amounts, promotes hydrogen atom transfer (HAT) from alcohols under electrochemical conditions through the generation of phthalimide‐N‐oxyl (PINO). In contrast with the well‐known electrochemical oxidation to their corresponding aldehydes or ketones, α‐alkoxy radicals were successfully coupled with oximes promoting a carbon–carbon bond‐forming event. This method allows the α‐functionalization of primary and secondary alcohols under simple, straightforward, and mild electrochemical reaction conditions in a single operation even in the presence of catalytic amounts of the HAT catalyst.
在这项工作中，我们描述了N -羟基邻苯二胺（NHPI）如何在催化量下，通过生成邻苯二胺- N -氧（PINO），在电化学条件下促进醇的氢原子转移（HAT）。与众所周知的电化学氧化成相应的醛或酮相反，α -烷氧基自由基成功地与肟结合，促进了碳-碳键形成事件。该方法允许在简单、直接、温和的电化学反应条件下，在一次操作中，即使在HAT催化剂的催化量存在下，也能实现伯醇和仲醇的α‐功能化。
{"title":"Electrochemical N‐hydroxyphthalimide Catalyzed Addition of α‐Alkoxy Radicals to Oxime Ethers","authors":"Rodrigo G. Enríquez, Juan S. Dato‐Santiago, Aitor Rivas‐Cobollo, José Alemán, Jose A. Fernández‐Salas","doi":"10.1002/adsc.70291","DOIUrl":"https://doi.org/10.1002/adsc.70291","url":null,"abstract":"In this work, we describe how N‐hydroxyphthalimide (NHPI), also under catalytic amounts, promotes hydrogen atom transfer (HAT) from alcohols under electrochemical conditions through the generation of phthalimide‐N‐oxyl (PINO). In contrast with the well‐known electrochemical oxidation to their corresponding aldehydes or ketones, α‐alkoxy radicals were successfully coupled with oximes promoting a carbon–carbon bond‐forming event. This method allows the α‐functionalization of primary and secondary alcohols under simple, straightforward, and mild electrochemical reaction conditions in a single operation even in the presence of catalytic amounts of the HAT catalyst.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"32 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146198904","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Geyang Song, Xiaoli Shi, Liu Yang, Jiameng Song, Xinyi Liu, Juan Fan, Dong Xue
The combination of photocatalysis and nickel catalysis has been effectively utilized in the esterification of carboxylic acids with aryl halides. In this work, we present an approach where the esterification of carboxylic acids with aryl halides is achieved without an external photocatalyst. An air‐stable Ni(II) complex and mild organic base are employed in the protocol, allowing for the esterification of aryl bromides and less reactive aryl chlorides with carboxylic acids. The method is also compatible with a variety of carboxylic acids, including formic acid and N ‐protected amino acid derivatives. Mechanistic investigations indicate that the carboxylic acid likely coordinates with nickel, and the homolysis of the NiO bond is the key step for couplings before undergoing a Ni(I)−Ni(III) catalytic cycle.
{"title":"Light‐Induced Nickel‐Carboxylate Facilitates C–O Coupling","authors":"Geyang Song, Xiaoli Shi, Liu Yang, Jiameng Song, Xinyi Liu, Juan Fan, Dong Xue","doi":"10.1002/adsc.70302","DOIUrl":"https://doi.org/10.1002/adsc.70302","url":null,"abstract":"The combination of photocatalysis and nickel catalysis has been effectively utilized in the esterification of carboxylic acids with aryl halides. In this work, we present an approach where the esterification of carboxylic acids with aryl halides is achieved without an external photocatalyst. An air‐stable Ni(II) complex and mild organic base are employed in the protocol, allowing for the esterification of aryl bromides and less reactive aryl chlorides with carboxylic acids. The method is also compatible with a variety of carboxylic acids, including formic acid and <jats:italic>N</jats:italic> ‐protected amino acid derivatives. Mechanistic investigations indicate that the carboxylic acid likely coordinates with nickel, and the homolysis of the NiO bond is the key step for couplings before undergoing a Ni(I)−Ni(III) catalytic cycle.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"111 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146198897","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tales A. C. Goulart, Roberto do Carmo Pinheiro, Gilson Zeni
Indoles represent a privileged scaffold in organic and medicinal chemistry, prompting continuous efforts toward efficient and versatile synthetic methodologies. In this review, we present a focused survey of recent advances (2020–2025) in the transition‐metal‐catalyzed synthesis of indoles from alkynes and nitrogen sources. Both intra‐ and intermolecular strategies are discussed, highlighting key developments involving cobalt, copper, gold, nickel, palladium, platinum, silver, rhodium, and ruthenium catalysts. Attention is given to mechanistic insights, with detailed discussions provided where necessary to enhance the reader's understanding of the underlying transformations. While this is not an exhaustive compilation of all literature available in the period, we emphasize the most representative and innovative contributions, acknowledging that space limitations may have excluded some high‐quality studies. This review aims to offer a clear and accessible overview of state‐of‐the‐art methodologies, serving as a valuable resource for researchers interested in the design and application of indole‐forming processes from readily available alkynes and nitrogen‐containing precursors.
{"title":"Exploring Transition‐Metal‐Catalyzed Pathways to Indoles From Alkynes and Nitrogen Compounds","authors":"Tales A. C. Goulart, Roberto do Carmo Pinheiro, Gilson Zeni","doi":"10.1002/adsc.70305","DOIUrl":"https://doi.org/10.1002/adsc.70305","url":null,"abstract":"Indoles represent a privileged scaffold in organic and medicinal chemistry, prompting continuous efforts toward efficient and versatile synthetic methodologies. In this review, we present a focused survey of recent advances (2020–2025) in the transition‐metal‐catalyzed synthesis of indoles from alkynes and nitrogen sources. Both intra‐ and intermolecular strategies are discussed, highlighting key developments involving cobalt, copper, gold, nickel, palladium, platinum, silver, rhodium, and ruthenium catalysts. Attention is given to mechanistic insights, with detailed discussions provided where necessary to enhance the reader's understanding of the underlying transformations. While this is not an exhaustive compilation of all literature available in the period, we emphasize the most representative and innovative contributions, acknowledging that space limitations may have excluded some high‐quality studies. This review aims to offer a clear and accessible overview of state‐of‐the‐art methodologies, serving as a valuable resource for researchers interested in the design and application of indole‐forming processes from readily available alkynes and nitrogen‐containing precursors.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"32 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146198903","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Despite notable advances achieved in the classic phosphine catalyzed allene–alkene [3 + 2] annulations, the scope of allenes mainly restrict to allenoates that bearing electron‐donating or neutral γ‐substituents. Reaction profile of electron‐withdrawing group‐substituted allenoates (e.g. allene‐1,3‐dicarboxylates (ADCs)) remained elusive yet in both symmetric and asymmetric patterns. Herein, we present a ( S )‐SITCP‐catalyzed [3 + 2] reaction of ADCs with rhodanine‐derived alkenes, providing efficient access of chiral spiro[rhodanine‐cyclopentene] derivatives in good yields (up to 98%) with excellent enantio‐ (up to 99% ee) and diastereoselectivity (up to > 20:1 dr). Notably, ADCs exhibited unparalleled reactivity and enantioselectivity against their γ ‐electron‐donating or neutral substituted analogs in this reaction.
{"title":"Phosphine‐Catalyzed Enantioselective [3 + 2] Annulation of Allene‐1,3‐Dicarboxylates with Rhodanine‐Derived Alkenes","authors":"Bo Wang, Zhiyang Cui, Honghao Sun, Jingrong Jin, Huizhe Lu, Leijie Zhou, Yanmei Xiong, Hongchao Guo","doi":"10.1002/adsc.70274","DOIUrl":"https://doi.org/10.1002/adsc.70274","url":null,"abstract":"Despite notable advances achieved in the classic phosphine catalyzed allene–alkene [3 + 2] annulations, the scope of allenes mainly restrict to allenoates that bearing electron‐donating or neutral γ‐substituents. Reaction profile of electron‐withdrawing group‐substituted allenoates (e.g. allene‐1,3‐dicarboxylates (ADCs)) remained elusive yet in both symmetric and asymmetric patterns. Herein, we present a ( <jats:italic>S</jats:italic> )‐SITCP‐catalyzed [3 + 2] reaction of ADCs with rhodanine‐derived alkenes, providing efficient access of chiral spiro[rhodanine‐cyclopentene] derivatives in good yields (up to 98%) with excellent enantio‐ (up to 99% ee) and diastereoselectivity (up to > 20:1 dr). Notably, ADCs exhibited unparalleled reactivity and enantioselectivity against their <jats:italic>γ</jats:italic> ‐electron‐donating or neutral substituted analogs in this reaction.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"77 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146198898","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Fang Wang, Xiaoyu Xie, Bo Ye, Lei Wang, Bihong Zhu
N ‐Heterocyclic compounds (NHCs) are widely encountered in natural products and pharmaceuticals with diverse biological activities, and constitute fundamental structural motifs in numerous organic compounds. Consequently, investigations into the synthesis and modification of these NHCs hold particular significance for chemists and pharmacologists. Of particularly note, multicomponents cascade cyclization reactions allow for creation of many bonds, even stereocenters, in a single step while maintaining predictable stereochemistry have drawn increasing interest, and its broader application has been reinforced by radical chemistry. Photocatalysis and electrocatalysis are two powerful strategies to promote the chemical reactions that have received tremendous attention in recent years. Moreover, photoelectrochemical, a fusion of electrochemical and photochemical, completes reactions that were once challenging, stands out as an effective tool. In these ways, a number of diversly NHCs are constructed. Herein, the most recent contributions on photocatalytic, electrocatalytic, and photoelectrocatalytic radical‐mediated three‐component cascade cyclization reactions to access NHCs are reviewed, providing more possible avenues for future work in this growing area.
N -杂环化合物（NHCs）广泛存在于具有多种生物活性的天然产物和药物中，是许多有机化合物的基本结构基序。因此，研究这些NHCs的合成和修饰对化学家和药理学家具有特别重要的意义。特别值得注意的是，多组分级联环化反应允许在一个步骤中产生许多键，甚至是立体中心，同时保持可预测的立体化学，这引起了越来越多的兴趣，其更广泛的应用已被自由基化学所加强。光催化和电催化是近年来备受关注的两种促进化学反应的有力手段。此外，光电化学，一种电化学和光化学的融合，完成了曾经具有挑战性的反应，作为一种有效的工具脱颖而出。通过这些方式，构建了许多不同的国家卫生保健中心。本文综述了光催化、电催化和光电催化自由基介导的三组分级联环化反应获得NHCs的最新研究成果，为这一不断发展的领域的未来工作提供了更多可能的途径。
{"title":"Photocatalytic, Electrocatalytic, and Photoelectrocatalytic Radical‐Mediated Three‐Component Cascade Cyclization Reactions: Facile Access to N ‐Heterocyclic Compounds","authors":"Fang Wang, Xiaoyu Xie, Bo Ye, Lei Wang, Bihong Zhu","doi":"10.1002/adsc.70306","DOIUrl":"https://doi.org/10.1002/adsc.70306","url":null,"abstract":"<jats:italic>N</jats:italic> ‐Heterocyclic compounds (NHCs) are widely encountered in natural products and pharmaceuticals with diverse biological activities, and constitute fundamental structural motifs in numerous organic compounds. Consequently, investigations into the synthesis and modification of these NHCs hold particular significance for chemists and pharmacologists. Of particularly note, multicomponents cascade cyclization reactions allow for creation of many bonds, even stereocenters, in a single step while maintaining predictable stereochemistry have drawn increasing interest, and its broader application has been reinforced by radical chemistry. Photocatalysis and electrocatalysis are two powerful strategies to promote the chemical reactions that have received tremendous attention in recent years. Moreover, photoelectrochemical, a fusion of electrochemical and photochemical, completes reactions that were once challenging, stands out as an effective tool. In these ways, a number of diversly NHCs are constructed. Herein, the most recent contributions on photocatalytic, electrocatalytic, and photoelectrocatalytic radical‐mediated three‐component cascade cyclization reactions to access NHCs are reviewed, providing more possible avenues for future work in this growing area.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"244 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146198901","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A visible‐light‐catalyzed chlorosulfonylation reaction of gem ‐difluoroalkenes has been successfully developed using sulfonyl chloride as both the sulfonyl group and chlorine source. The reaction proceeds under mild, additive‐free conditions, generating α , α ‐difluoromethyl‐ β ‐chlorosulfones with excellent regioselectivity and broad substrate scope. The β ‐chlorosulfone product serves as versatile intermediate, readily converting into valuable derivatives such as β ‐azido sulfone. This method provides rapid access to functional fluorinated scaffolds relevant to medicinal chemistry.
{"title":"Photoredox‐Catalyzed Chlorosulfonylation of gem ‐Difluoroalkenes","authors":"Raheel Ahmad, Yibo Tian, Tongtong Wang, Sakhawat Shah, Liqiao Han, Fengqian Zhao, Junliang Wu","doi":"10.1002/adsc.70311","DOIUrl":"https://doi.org/10.1002/adsc.70311","url":null,"abstract":"A visible‐light‐catalyzed chlorosulfonylation reaction of <jats:italic>gem</jats:italic> ‐difluoroalkenes has been successfully developed using sulfonyl chloride as both the sulfonyl group and chlorine source. The reaction proceeds under mild, additive‐free conditions, generating <jats:italic>α</jats:italic> , <jats:italic>α</jats:italic> ‐difluoromethyl‐ <jats:italic>β</jats:italic> ‐chlorosulfones with excellent regioselectivity and broad substrate scope. The <jats:italic>β</jats:italic> ‐chlorosulfone product serves as versatile intermediate, readily converting into valuable derivatives such as <jats:italic>β</jats:italic> ‐azido sulfone. This method provides rapid access to functional fluorinated scaffolds relevant to medicinal chemistry.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"19 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146198905","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A new class of sulfide‐based catalysts that enable hydrogen atom transfer (HAT) under visible‐light‐driven photoredox conditions is reported. Based on the potential of indirect HAT processes, alkyl aryl sulfides that undergo single‐electron oxidation to generate radical cations were designed as candidate HAT catalysts. A wide variety of alkyl aryl sulfides exhibit catalytic activity, promoting the CH alkylation of a broad range of substrates, including alcohols, ethers, hydrocarbons, and aldehydes, in the presence of an acridinium photocatalyst. The reactions proceed under mild conditions without additional bases or additives. Mechanistic studies, including fluorescence quenching and deuterium labeling, indicate a pathway involving radical cation intermediates. DFT calculations indicate that the 2‐thiazolyl structure on the sulfide enhances the catalyst activity by shifting the HAT from an S ‐centered pathway to an N ‐centered pathway. This study establishes sulfides as modular platforms for photoredox‐mediated HAT catalysis.
{"title":"Expanding the Toolbox for Hydrogen Atom Transfer Catalysis: Sulfides as Structurally Diverse Catalysts Under Photoredox Conditions","authors":"Tetsuya Sengoku, Shun Nishioka, Yu Kokoda, Yoshifumi Noguchi, Toshiyasu Inuzuka","doi":"10.1002/adsc.70293","DOIUrl":"https://doi.org/10.1002/adsc.70293","url":null,"abstract":"A new class of sulfide‐based catalysts that enable hydrogen atom transfer (HAT) under visible‐light‐driven photoredox conditions is reported. Based on the potential of indirect HAT processes, alkyl aryl sulfides that undergo single‐electron oxidation to generate radical cations were designed as candidate HAT catalysts. A wide variety of alkyl aryl sulfides exhibit catalytic activity, promoting the CH alkylation of a broad range of substrates, including alcohols, ethers, hydrocarbons, and aldehydes, in the presence of an acridinium photocatalyst. The reactions proceed under mild conditions without additional bases or additives. Mechanistic studies, including fluorescence quenching and deuterium labeling, indicate a pathway involving radical cation intermediates. DFT calculations indicate that the 2‐thiazolyl structure on the sulfide enhances the catalyst activity by shifting the HAT from an <jats:italic>S</jats:italic> ‐centered pathway to an <jats:italic>N</jats:italic> ‐centered pathway. This study establishes sulfides as modular platforms for photoredox‐mediated HAT catalysis.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"126 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146198902","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：