Y. Bharath Chaithanya Kumar, Polasani Samatha, Deekshia Bhattachan, Raju Adepu
Herein, we have reported chemodivergent Diels–Alder reaction of allene formed in situ via a base-catalyzed alkyne-to-allene isomerization for the synthesis of fused carbazoles in a cascade reaction manner. The regioselectivity of the cycloaddition reaction was achieved using copper additives. The present cascade reaction involved Knoevenagel condensation, in situ allene formation, regioselective Diels–Alder reaction, followed by oxidation or aromatization.
{"title":"Regioselective Synthesis of Carbazoles via Chemodivergent Cascade Intramolecular [4 + 2] Annulation","authors":"Y. Bharath Chaithanya Kumar, Polasani Samatha, Deekshia Bhattachan, Raju Adepu","doi":"10.1002/adsc.70258","DOIUrl":"https://doi.org/10.1002/adsc.70258","url":null,"abstract":"Herein, we have reported chemodivergent Diels–Alder reaction of allene formed in situ via a base-catalyzed alkyne-to-allene isomerization for the synthesis of fused carbazoles in a cascade reaction manner. The regioselectivity of the cycloaddition reaction was achieved using copper additives. The present cascade reaction involved Knoevenagel condensation, in situ allene formation, regioselective Diels–Alder reaction, followed by oxidation or aromatization.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"1 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145651261","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}
Development of methods with newer strategies for organic radical generation has been a major thrust area of synthetic organic chemistry in the last decade and a half. Often, the radical generation is aided by photoirradiation or electrochemical activation. Phosphinium radical cations, accessed by single electron oxidation or hydrogen atom abstraction, have recently emerged as a unique tool to furnish a variety of organic radicals leading to diverse functional group installations, reductions, cyclization, rearrangements, etc. Herein, we provide an account for the working model of this chemistry and the recent progress of this elegant approach with exciting prospects in the future.
{"title":"Emergence of Phosphinium Radical Cations as Intermediates for Organic Radical Generation","authors":"Prasun Sinha, Priyasha Dey, Yash Aneja, Akhilesh Singh Tilara, Abhishek Dewanji","doi":"10.1002/adsc.70243","DOIUrl":"https://doi.org/10.1002/adsc.70243","url":null,"abstract":"Development of methods with newer strategies for organic radical generation has been a major thrust area of synthetic organic chemistry in the last decade and a half. Often, the radical generation is aided by photoirradiation or electrochemical activation. Phosphinium radical cations, accessed by single electron oxidation or hydrogen atom abstraction, have recently emerged as a unique tool to furnish a variety of organic radicals leading to diverse functional group installations, reductions, cyclization, rearrangements, etc. Herein, we provide an account for the working model of this chemistry and the recent progress of this elegant approach with exciting prospects in the future.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"10 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145651167","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}
Anthony Saint Pol, Maxime Roger, Alexis Mifleur, Pauline Loxq, Laëtitia Chausset‐Boissarie, Aurélien Béthegnies, Maël Penhoat, Isabelle Suisse, Mathieu Sauthier
In the presence of a catalytic amount (1 mol%) of Ni(cod) 2 and dppmb (1,2‐bis(diphenylphosphinomethyl)benzene)), a three‐component coupling reaction between industrially available aldehydes, buta‐1,3‐diene, and amines leads to the formation of variety of homoallylic alcohols with a highly functionalized 5‐aminopent‐3‐en‐1‐ol structure. The reaction proceeds with 100% atom economy under mild conditions (80 °C) in isopropanol as solvent. The process accommodates both aliphatic and aromatic aldehydes in combination with cyclic and acyclic secondary dialkyl amines, demonstrating a broad substrates scope. Reaction monitoring shows that the initial rate of the reaction is 39 h −1 , and the process reaches a maximum within 3 h of reaction at 80 °C. A competitive reaction has been identified as the hydroamination of 1,3‐butadiene that affords light butenylamines. The key mechanistic feature of the three‐component nickel‐catalyzed reaction is the formation of an η3 : η1 ‐allylalkoxy nickel (II) intermediate obtained from the oxidative coupling reaction between a low valent nickel (0) precursor, buta‐1,3‐diene, and an aldehyde. The amine subsequently reacts as a nucleophile with the electrophilic allyl moiety of this intermediate, while the alkoxy group acts as an internal base facilitating proton transfer that enables the synthesis of 5‐aminopent‐3‐en‐1‐ol derivatives without any base and salt formation.
{"title":"Synthesis of Functionalized Homoallylic Alcohols via a Salt‐Free Three‐Component Nickel‐Catalyzed Coupling Reaction","authors":"Anthony Saint Pol, Maxime Roger, Alexis Mifleur, Pauline Loxq, Laëtitia Chausset‐Boissarie, Aurélien Béthegnies, Maël Penhoat, Isabelle Suisse, Mathieu Sauthier","doi":"10.1002/adsc.70183","DOIUrl":"https://doi.org/10.1002/adsc.70183","url":null,"abstract":"In the presence of a catalytic amount (1 mol%) of Ni(cod) <jats:sub>2</jats:sub> and dppmb (1,2‐bis(diphenylphosphinomethyl)benzene)), a three‐component coupling reaction between industrially available aldehydes, buta‐1,3‐diene, and amines leads to the formation of variety of homoallylic alcohols with a highly functionalized 5‐aminopent‐3‐en‐1‐ol structure. The reaction proceeds with 100% atom economy under mild conditions (80 °C) in isopropanol as solvent. The process accommodates both aliphatic and aromatic aldehydes in combination with cyclic and acyclic secondary dialkyl amines, demonstrating a broad substrates scope. Reaction monitoring shows that the initial rate of the reaction is 39 h <jats:sup>−1</jats:sup> , and the process reaches a maximum within 3 h of reaction at 80 °C. A competitive reaction has been identified as the hydroamination of 1,3‐butadiene that affords light butenylamines. The key mechanistic feature of the three‐component nickel‐catalyzed reaction is the formation of an <jats:italic>η</jats:italic> <jats:sup>3</jats:sup> : <jats:italic>η</jats:italic> <jats:sup>1</jats:sup> ‐allylalkoxy nickel (II) intermediate obtained from the oxidative coupling reaction between a low valent nickel (0) precursor, buta‐1,3‐diene, and an aldehyde. The amine subsequently reacts as a nucleophile with the electrophilic allyl moiety of this intermediate, while the alkoxy group acts as an internal base facilitating proton transfer that enables the synthesis of 5‐aminopent‐3‐en‐1‐ol derivatives without any base and salt formation.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"68 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145651169","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 recent years, special emphasis has been put on spirocyclization reactions of biaryl ynones since these strategies offer versatile platforms for introducing various important functional groups into spirocyclic frameworks in a step‐economical manner, which is conducive to drug discovery. In this regard, various functionalized spiro[5.5]trienones and 3,3‐spiroindanones have been synthesized via the radical, radical cation, or electrophilic process promoted by thermal, photochemical, and electrochemical means. In this invited review, we systematically summarize the spirocyclization reactions of biaryl ynones with diverse organic precursors, highlighting the reaction patterns, mechanistic insights, and synthetic applications.
{"title":"Recent Advances in Spirocyclization Reactions of Biaryl Ynones","authors":"Luping Zheng, Yunfei Tian, Weijun Fu, Zejiang Li","doi":"10.1002/adsc.70160","DOIUrl":"https://doi.org/10.1002/adsc.70160","url":null,"abstract":"In recent years, special emphasis has been put on spirocyclization reactions of biaryl ynones since these strategies offer versatile platforms for introducing various important functional groups into spirocyclic frameworks in a step‐economical manner, which is conducive to drug discovery. In this regard, various functionalized spiro[5.5]trienones and 3,3‐spiroindanones have been synthesized via the radical, radical cation, or electrophilic process promoted by thermal, photochemical, and electrochemical means. In this invited review, we systematically summarize the spirocyclization reactions of biaryl ynones with diverse organic precursors, highlighting the reaction patterns, mechanistic insights, and synthetic applications.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"57 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145613679","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}
Qingqing Shao, Guoqing Huang, Tong Wang, Ming Yang, Daoshan Yang, Xiubin Bu, Xiaobo Yang, Zhen Zhao
Metal‐covalent organic frameworks (M‐COFs) are a class of crystalline porous materials formed by the coordination bonds between metals centers and covalent organic frameworks (COFs). They retain the characteristics of COFs while providing exposed metal active sites. Compared with homogeneous transition metal catalysts, M‐COFs exhibit superior catalytic activity, high stability, tunability, high specific surface area, and ordered pore channels. More importantly, due to their heterogeneous nature, M‐COFs catalysts can be reused multiple times conveniently, avoiding the residual presence of transition metals and reducing resource and environmental consumption. This review introduces the general design strategies and synthesis methods of M‐COFs, briefly discusses the intrinsic relationship between their structure and catalytic activity, and focuses on summarizing their applications in organic transformations. It also highlights the advantages and challenges of M‐COFs in catalyzing organic transformation reactions and discusses the future development directions in this field.
{"title":"Metal–Covalent Organic Frameworks: Synthetic Strategies and Catalytic Applications in Organic Transformations","authors":"Qingqing Shao, Guoqing Huang, Tong Wang, Ming Yang, Daoshan Yang, Xiubin Bu, Xiaobo Yang, Zhen Zhao","doi":"10.1002/adsc.70237","DOIUrl":"https://doi.org/10.1002/adsc.70237","url":null,"abstract":"Metal‐covalent organic frameworks (M‐COFs) are a class of crystalline porous materials formed by the coordination bonds between metals centers and covalent organic frameworks (COFs). They retain the characteristics of COFs while providing exposed metal active sites. Compared with homogeneous transition metal catalysts, M‐COFs exhibit superior catalytic activity, high stability, tunability, high specific surface area, and ordered pore channels. More importantly, due to their heterogeneous nature, M‐COFs catalysts can be reused multiple times conveniently, avoiding the residual presence of transition metals and reducing resource and environmental consumption. This review introduces the general design strategies and synthesis methods of M‐COFs, briefly discusses the intrinsic relationship between their structure and catalytic activity, and focuses on summarizing their applications in organic transformations. It also highlights the advantages and challenges of M‐COFs in catalyzing organic transformation reactions and discusses the future development directions in this field.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"29 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145613680","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 novel photochemical trifluoromethylation/cyclization of unactivated alkenes to synthesize trifluoromethyl‐substituted quinazolinones with trifluoromethylsulfonyl‐pyridinium salt (TFSP) is achieved under catalyst‐free conditions. Mechanistic studies reveal that an electron‐donating‐accepting complex is formed between the quinazolinone and TFSP, making this the first example of TFSP‐based trifluoromethylation conducted in the absence of expensive iridium photocatalysts.
{"title":"Photocatalyst‐Free Photochemical Trifluoromethylation/Cyclization of Unactivated Alkenes: Synthesis of Trifluoromethyl‐Substituted Quinazolinones","authors":"Ziqin Zhang, Yu Zhao, Qianqian Feng, Guoyao Jin, Kui Lu, Xia Zhao","doi":"10.1002/adsc.70144","DOIUrl":"https://doi.org/10.1002/adsc.70144","url":null,"abstract":"A novel photochemical trifluoromethylation/cyclization of unactivated alkenes to synthesize trifluoromethyl‐substituted quinazolinones with trifluoromethylsulfonyl‐pyridinium salt (TFSP) is achieved under catalyst‐free conditions. Mechanistic studies reveal that an electron‐donating‐accepting complex is formed between the quinazolinone and TFSP, making this the first example of TFSP‐based trifluoromethylation conducted in the absence of expensive iridium photocatalysts.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"24 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145613683","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 series of chiral potassium Brønsted bases containing 3,3′‐substituted 1,1′‐bi‐2‐naphthol‐based chiral crown ethers are demonstrated as sustainable metal catalysts for a tandem allylic isomerization/asymmetric aldol–Tishchenko reaction. The crown ether creates an effective chiral environment around the potassium cation, yielding diverse 1,3‐diols containing three contiguous stereogenic centers with excellent diastereoselectivity and high enantioselectivity. This system allows the use of allylic alcohols instead of enolizable ketones as nucleophiles, thus broadening the synthetic applicability of this reaction.
{"title":"Chiral Potassium Brønsted Base‐Catalyzed Stereoselective Synthesis of 1,3‐Diols via a Tandem Allylic Isomerization/Asymmetric Aldol–Tishchenko Reaction","authors":"Hiroki Ishikawa, Masahiro Sai","doi":"10.1002/adsc.70108","DOIUrl":"https://doi.org/10.1002/adsc.70108","url":null,"abstract":"A series of chiral potassium Brønsted bases containing 3,3′‐substituted 1,1′‐bi‐2‐naphthol‐based chiral crown ethers are demonstrated as sustainable metal catalysts for a tandem allylic isomerization/asymmetric aldol–Tishchenko reaction. The crown ether creates an effective chiral environment around the potassium cation, yielding diverse 1,3‐diols containing three contiguous stereogenic centers with excellent diastereoselectivity and high enantioselectivity. This system allows the use of allylic alcohols instead of enolizable ketones as nucleophiles, thus broadening the synthetic applicability of this reaction.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"198200 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145613681","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}
Pietro Ronco , Antonia Simi , Enrico Lunghi , Emanuele Casali , Giovanni Lenardon , Alessio Porta , Giuseppe Zanoni
A sustainable and efficient electrochemical method for the direct oxidative lactonization of benzylic alcohols, enabling rapid access to isobenzofuran‐1(3H)‐ones (phthalides) is presented. This electrocatalytic transformation leverages N‐hydroxyphthalimide as a redox mediator under mild, metal‐free conditions, offering an environmentally friendly alternative to traditional oxidation protocols. The method demonstrates broad substrate scope and delivers phthalide derivatives consistently in good to excellent yields. Mechanistic studies, combining cyclic voltammetry and density functional theory calculations, support a radical‐mediated hydrogen atom transfer mechanism driven by phthalimide‐N‐oxyl radicals. Importantly, the utility of the protocol extends beyond model substrates: it is successfully applied to the synthesis of pharmaceutically relevant compounds, including talopram and a key intermediate for a neuropeptide Y5 receptor antagonist. Overall, this work underscores the power of electrosynthesis in modern organic chemistry, merging green chemistry principles with synthetic efficiency.
提出了一种可持续的、高效的苯基醇直接氧化内酯化的电化学方法，可以快速获得异苯并呋喃-1(3H)- 1（邻苯二甲酸酯）。这种电催化转化利用n -羟基邻苯二胺作为氧化还原介质，在温和、无金属的条件下，为传统氧化方案提供了一种环保的替代方案。该方法证明了广泛的底物范围，并提供了苯酞衍生物一致良好的收率。结合循环伏安法和密度泛函理论计算的机理研究支持了邻苯二胺- n -氧自由基驱动的自由基介导的氢原子转移机制。重要的是，该方案的实用性超出了模型底物：它成功地应用于药学相关化合物的合成，包括他洛普兰和神经肽Y5受体拮抗剂的关键中间体。总的来说，这项工作强调了电合成在现代有机化学中的力量，将绿色化学原理与合成效率相结合。
{"title":"Electrocatalytic Dehydrogenative Lactonization of Benzylic Alcohols: A Sustainable Access to Phthalides via N‐hydroxyphthalimide Mediation","authors":"Pietro Ronco , Antonia Simi , Enrico Lunghi , Emanuele Casali , Giovanni Lenardon , Alessio Porta , Giuseppe Zanoni","doi":"10.1002/adsc.70138","DOIUrl":"10.1002/adsc.70138","url":null,"abstract":"<div><div>A sustainable and efficient electrochemical method for the direct oxidative lactonization of benzylic alcohols, enabling rapid access to isobenzofuran‐1(3H)‐ones (phthalides) is presented. This electrocatalytic transformation leverages <em>N</em>‐hydroxyphthalimide as a redox mediator under mild, metal‐free conditions, offering an environmentally friendly alternative to traditional oxidation protocols. The method demonstrates broad substrate scope and delivers phthalide derivatives consistently in good to excellent yields. Mechanistic studies, combining cyclic voltammetry and density functional theory calculations, support a radical‐mediated hydrogen atom transfer mechanism driven by phthalimide‐<em>N</em>‐oxyl radicals. Importantly, the utility of the protocol extends beyond model substrates: it is successfully applied to the synthesis of pharmaceutically relevant compounds, including talopram and a key intermediate for a neuropeptide Y5 receptor antagonist. Overall, this work underscores the power of electrosynthesis in modern organic chemistry, merging green chemistry principles with synthetic efficiency.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 22","pages":"Article e70138"},"PeriodicalIF":4.0,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145182982","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}
Yi‐Yun Huang , Xin‐Yu Lin , Run Xiong , Bi‐Yuan Yang , Ning Ma , Ru‐An Chi , Zhi‐Peng Guan , Jian Lv , Zhi‐Bing Dong
In recent years, with the rapid development of photocatalytic and electrocatalytic technologies, multicomponent reaction systems employing carbon disulfide (CS2) or elemental sulfur (S8) as key reagents have emerged as a burgeoning research frontier in synthetic chemistry. This review systematically summarizes recent advances in the development of photocatalytic and electrocatalytic multicomponent reaction systems employing carbon disulfide or elemental sulfur as key sulfur‐containing reagents, with particular emphasis on mechanistic insights, catalytic innovation, and sustainable synthetic applications.
{"title":"Recent Advances In The Multicomponent Reactions of CS2 or S8 Under Photo/Electrocatalysis","authors":"Yi‐Yun Huang , Xin‐Yu Lin , Run Xiong , Bi‐Yuan Yang , Ning Ma , Ru‐An Chi , Zhi‐Peng Guan , Jian Lv , Zhi‐Bing Dong","doi":"10.1002/adsc.70129","DOIUrl":"10.1002/adsc.70129","url":null,"abstract":"<div><div>In recent years, with the rapid development of photocatalytic and electrocatalytic technologies, multicomponent reaction systems employing carbon disulfide (CS<sub>2</sub>) or elemental sulfur (S<sub>8</sub>) as key reagents have emerged as a burgeoning research frontier in synthetic chemistry. This review systematically summarizes recent advances in the development of photocatalytic and electrocatalytic multicomponent reaction systems employing carbon disulfide or elemental sulfur as key sulfur‐containing reagents, with particular emphasis on mechanistic insights, catalytic innovation, and sustainable synthetic applications.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 22","pages":"Article e70129"},"PeriodicalIF":4.0,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145083945","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}
Yubo Long , Meilin Tang , Yixin Liao , Shiqi Xu , Haobing Deng , Jinyao Liu , Peiru Chen , Jinwu Zhao , Wenfang Xiong
Methylation reactions have extraordinary value in organic chemistry, ranging from the assembly of structurally diverse organic functional chemicals to the introduction of methyl groups into pharmaceutical and agrochemical intermediates. In the context of sustainable chemistry, carbon dioxide (CO2) has emerged as an idea and alternative greener C1 source. As a result, reductive methylation strategies utilizing CO2 as a methylating agent have garnered substantial research interest in recent decades, particularly for synthesizing methylated derivatives, compounds with broad applications in drug discovery and agrochemical development. In this review, reductive methylations using CO2 as C1 synthon have been summarized and discussed in detail with focus on metal‐catalyzed C/N‐methylation reactions, base catalyzed C/N‐methylation reactions, ionic liquids catalyzed C/N‐methylation reactions, and catalyst‐free C/N‐methylation reactions based on various reductants. We also elucidate substrate compatibility in these reductive methylations, competing side reactions, and representative reaction mechanisms. Furthermore, conclusions and future trends are depicted finally in this review.
{"title":"Advancements and Challenges in Reductive Methylation of Carbon Dioxide","authors":"Yubo Long , Meilin Tang , Yixin Liao , Shiqi Xu , Haobing Deng , Jinyao Liu , Peiru Chen , Jinwu Zhao , Wenfang Xiong","doi":"10.1002/adsc.70054","DOIUrl":"10.1002/adsc.70054","url":null,"abstract":"<div><div>Methylation reactions have extraordinary value in organic chemistry, ranging from the assembly of structurally diverse organic functional chemicals to the introduction of methyl groups into pharmaceutical and agrochemical intermediates. In the context of sustainable chemistry, carbon dioxide (CO<sub>2</sub>) has emerged as an idea and alternative greener C1 source. As a result, reductive methylation strategies utilizing CO<sub>2</sub> as a methylating agent have garnered substantial research interest in recent decades, particularly for synthesizing methylated derivatives, compounds with broad applications in drug discovery and agrochemical development. In this review, reductive methylations using CO<sub>2</sub> as C1 synthon have been summarized and discussed in detail with focus on metal‐catalyzed C/N‐methylation reactions, base catalyzed C/N‐methylation reactions, ionic liquids catalyzed C/N‐methylation reactions, and catalyst‐free C/N‐methylation reactions based on various reductants. We also elucidate substrate compatibility in these reductive methylations, competing side reactions, and representative reaction mechanisms. Furthermore, conclusions and future trends are depicted finally in this review.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 22","pages":"Article e70054"},"PeriodicalIF":4.0,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195404","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}
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