Taorui Qu , Sheng Yu , Dr. Changduo Pan , Prof. Jin‐Tao Yu
A visible‐light‐induced alkylation of azauracils was developed via the site‐selective 1,5‐hydrogen atom transfer of hydroxamic acid derivatives. The cross‐dehydrogenative coupling reaction between C(sp2)─H bond in azauracils and the γ‐C(sp3)─H bond in hydroxamic acid derivatives was involved. Notable features of this protocol include its mild and metal‐free reaction conditions, significant atom/step efficiency, broad substrate scope, and its application in the late‐stage modification of pharmaceutical compounds.
{"title":"Visible‐Light‐Promoted C─H Alkylation of Azauracils Via a Site‐Selective 1,5‐Hydrogen Atom Transfer‐Induced Cross‐Dehydrogenative Coupling","authors":"Taorui Qu , Sheng Yu , Dr. Changduo Pan , Prof. Jin‐Tao Yu","doi":"10.1002/ajoc.70201","DOIUrl":"10.1002/ajoc.70201","url":null,"abstract":"<div><div>A visible‐light‐induced alkylation of azauracils was developed via the site‐selective 1,5‐hydrogen atom transfer of hydroxamic acid derivatives. The cross‐dehydrogenative coupling reaction between C(sp<sup>2</sup>)─H bond in azauracils and the γ‐C(sp<sup>3</sup>)─H bond in hydroxamic acid derivatives was involved. Notable features of this protocol include its mild and metal‐free reaction conditions, significant atom/step efficiency, broad substrate scope, and its application in the late‐stage modification of pharmaceutical compounds.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 11","pages":"Article e70201"},"PeriodicalIF":2.7,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145500960","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}
Nilam Patil , Priyanka R. Angarkhe , Prof. Bhalchandra M. Bhanage
A sustainable electrochemical protocol has been established for the synthesis of fused polycyclic heteroarenes, which are valuable motifs in medicinal chemistry and materials science. This transformation employs a ruthenium‐catalyzed annulation of quinazolinones with alkynes, driven by the application of electric current. Unlike conventional oxidative annulations that require stoichiometric additives or toxic oxidants, this method relies on electricity as a green oxidant, producing molecular hydrogen as the sole by‐product. The reaction proceeds efficiently under ligand‐free conditions, offering a simple and operationally convenient strategy with excellent atom economy. Importantly, the protocol exhibits broad substrate tolerance, accommodating a wide variety of functional groups on both partners, and consistently delivers the desired fused heteroarenes in synthetically useful yields. Overall, this electrochemical approach provides an environmentally benign and practical alternative to traditional oxidative methodologies, highlighting the potential of electrocatalysis in advancing sustainable heteroarene synthesis.
{"title":"Sustainable Electrochemical Access to Fused Quinazolinones Through Ruthenium Catalysis","authors":"Nilam Patil , Priyanka R. Angarkhe , Prof. Bhalchandra M. Bhanage","doi":"10.1002/ajoc.70206","DOIUrl":"10.1002/ajoc.70206","url":null,"abstract":"<div><div>A sustainable electrochemical protocol has been established for the synthesis of fused polycyclic heteroarenes, which are valuable motifs in medicinal chemistry and materials science. This transformation employs a ruthenium‐catalyzed annulation of quinazolinones with alkynes, driven by the application of electric current. Unlike conventional oxidative annulations that require stoichiometric additives or toxic oxidants, this method relies on electricity as a green oxidant, producing molecular hydrogen as the sole by‐product. The reaction proceeds efficiently under ligand‐free conditions, offering a simple and operationally convenient strategy with excellent atom economy. Importantly, the protocol exhibits broad substrate tolerance, accommodating a wide variety of functional groups on both partners, and consistently delivers the desired fused heteroarenes in synthetically useful yields. Overall, this electrochemical approach provides an environmentally benign and practical alternative to traditional oxidative methodologies, highlighting the potential of electrocatalysis in advancing sustainable heteroarene synthesis.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 11","pages":"Article e70206"},"PeriodicalIF":2.7,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145501040","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}
Chaoyue Sun , Xuan Zhang , Shuodi Fei , Ge Jin , Qin Zhang , Wang Geng , Yun Han , Ying Jia , Prof. Dr. Peiwei Gong , Dr. Mianran Chao , Dr. Duyi Shen
The development of catalyst‐ and metal‐free methods for vicinal chloro‐functionalization of olefins could provide a highly desirable approach to value‐added organic halides. In this study, the chloro‐alkoxylation of alkenes was achieved at room temperature by using tert‐butyl hypochlorite (tBuOCl) as the electrophilic chlorination reagent and alcohols as the nucleophiles. This reaction system could cover a wide range of substrates that aromatic and aliphatic terminal, aromatic and aliphatic internal alkenes were transformed into the corresponding β‐chloroethyl ether products with good yield and regioselectivity, probably following the Markovnikov addition process. In addition, the reaction of α,β‐unsaturated ketone, ester, and acids that were less studied before could afford the major anti‐products in good diastereoselectivity and high yields. Furthermore, this method could be applied to the late‐stage functionalization of complex substrates bearing naturally occurring scaffolds. This work established a simple, atom‐economic, easy‐handling, and synthetic valuable protocol for the transformation of bulk chemicals like olefins and alcohols to access various β‐chloroethyl ethers, including 30 new compounds with a preferred chlorination reagent.
{"title":"A Catalyst‐Free, Transition‐Metal‐Free, and Selective Chloro‐Alkoxylation of Olefins with Alcohols and tert‐Butyl Hypochlorite","authors":"Chaoyue Sun , Xuan Zhang , Shuodi Fei , Ge Jin , Qin Zhang , Wang Geng , Yun Han , Ying Jia , Prof. Dr. Peiwei Gong , Dr. Mianran Chao , Dr. Duyi Shen","doi":"10.1002/ajoc.70190","DOIUrl":"10.1002/ajoc.70190","url":null,"abstract":"<div><div>The development of catalyst‐ and metal‐free methods for vicinal chloro‐functionalization of olefins could provide a highly desirable approach to value‐added organic halides. In this study, the chloro‐alkoxylation of alkenes was achieved at room temperature by using <em>tert</em>‐butyl hypochlorite (<em>t</em>BuOCl) as the electrophilic chlorination reagent and alcohols as the nucleophiles. This reaction system could cover a wide range of substrates that aromatic and aliphatic terminal, aromatic and aliphatic internal alkenes were transformed into the corresponding β‐chloroethyl ether products with good yield and regioselectivity, probably following the Markovnikov addition process. In addition, the reaction of α,β‐unsaturated ketone, ester, and acids that were less studied before could afford the major anti‐products in good diastereoselectivity and high yields. Furthermore, this method could be applied to the late‐stage functionalization of complex substrates bearing naturally occurring scaffolds. This work established a simple, atom‐economic, easy‐handling, and synthetic valuable protocol for the transformation of bulk chemicals like olefins and alcohols to access various β‐chloroethyl ethers, including 30 new compounds with a preferred chlorination reagent.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 11","pages":"Article e70190"},"PeriodicalIF":2.7,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145500847","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}
Kinga Piotrowska , Jan Rzepiela , Dr. Sebastian Baś
The present study investigates the versatility of visible‐light‐initiated decarboxylation of amino acids, resulting in the formation of an α‐amino radical. Herein, we have delineated the comprehensive scope and limitations of Giese's addition to electron‐deficient alkenes. Furthermore, we have demonstrated the extendibility of this concept to electron‐rich styrene derivatives. This strategy has been demonstrated to suppress other reactions recently reported for this type of reagents, thereby providing target products with high yields. The designed methodology facilitates the functionalisation of bioactive molecules during the advanced stages of the process. We have illustrated that the developed transformation has significant potential for further applications in the synthesis of bicyclic alkaloid skeletons.
{"title":"Investigation into the Utility of Visible‐Light‐Initiated Decarboxylative Radical Addition of Amino Acids to Alkenes, With Applications in the Synthesis of Alkaloid Scaffolds","authors":"Kinga Piotrowska , Jan Rzepiela , Dr. Sebastian Baś","doi":"10.1002/ajoc.202500609","DOIUrl":"10.1002/ajoc.202500609","url":null,"abstract":"<div><div>The present study investigates the versatility of visible‐light‐initiated decarboxylation of amino acids, resulting in the formation of an α‐amino radical. Herein, we have delineated the comprehensive scope and limitations of Giese's addition to electron‐deficient alkenes. Furthermore, we have demonstrated the extendibility of this concept to electron‐rich styrene derivatives. This strategy has been demonstrated to suppress other reactions recently reported for this type of reagents, thereby providing target products with high yields. The designed methodology facilitates the functionalisation of bioactive molecules during the advanced stages of the process. We have illustrated that the developed transformation has significant potential for further applications in the synthesis of bicyclic alkaloid skeletons.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 11","pages":"Article e00609"},"PeriodicalIF":2.7,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145501049","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}
Non‐covalent interaction‐driven synthetic strategies have revolutionized carbohydrate chemistry. Halogen bonding donors are expected to significantly improve the efficiency and selectivity of carbohydrate synthesis by precisely modulating weak intermolecular interactions. In this study, we described a thiocyanato‐enhanced neutral monodentate halogen bonding donor demonstrating high efficacy in converting 2,3‐unsaturated glycosyl acetates to 2,3‐unsaturated glycosides. This donor, with cost‐efficiency and operational robustness, exhibited great potential for industrial applications. Density functional theory calculations confirmed that the iodine‐oxygen bond lengths and angles in the donor‐substrate complex align with characteristic halogen bonding parameters. Mechanistic studies further elucidated the impact of donor structural architecture and stoichiometric ratios on glycosylation efficiency. This halogen bonding donor offers a new option for constructing biologically active carbohydrate molecules.
{"title":"Halogen Bonding‐Mediated Glycosylation of 2,3‐Unsaturated Glycosyl Acetates via NCSCH2Cl/KI","authors":"Xiaojun Li , Qing Li , Yali Liu , Wenjiao Yuan","doi":"10.1002/ajoc.202500527","DOIUrl":"10.1002/ajoc.202500527","url":null,"abstract":"<div><div>Non‐covalent interaction‐driven synthetic strategies have revolutionized carbohydrate chemistry. Halogen bonding donors are expected to significantly improve the efficiency and selectivity of carbohydrate synthesis by precisely modulating weak intermolecular interactions. In this study, we described a thiocyanato‐enhanced neutral monodentate halogen bonding donor demonstrating high efficacy in converting 2,3‐unsaturated glycosyl acetates to 2,3‐unsaturated glycosides. This donor, with cost‐efficiency and operational robustness, exhibited great potential for industrial applications. Density functional theory calculations confirmed that the iodine‐oxygen bond lengths and angles in the donor‐substrate complex align with characteristic halogen bonding parameters. Mechanistic studies further elucidated the impact of donor structural architecture and stoichiometric ratios on glycosylation efficiency. This halogen bonding donor offers a new option for constructing biologically active carbohydrate molecules.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 11","pages":"Article e00527"},"PeriodicalIF":2.7,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145500886","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}
Myungho Jung , Sunhee Lee , Dohui Ku , Dageum Kang , Prof. Dr. Ikyon Kim
A highly efficient domino process consisting of conjugate substitution, nucleophilic addition, and cycloisomerization from the reaction of enaminonitrile with propargylamine allowed for a successive double ring closure to afford a densely functionalized imidazo[1,2‐a]pyridine through formation of three C─N bonds.
{"title":"Synthesis of Poly‐Substituted Imidazo[1,2‐a]Pyridines via a Double Annulation Strategy","authors":"Myungho Jung , Sunhee Lee , Dohui Ku , Dageum Kang , Prof. Dr. Ikyon Kim","doi":"10.1002/ajoc.70175","DOIUrl":"10.1002/ajoc.70175","url":null,"abstract":"<div><div>A highly efficient domino process consisting of conjugate substitution, nucleophilic addition, and cycloisomerization from the reaction of enaminonitrile with propargylamine allowed for a successive double ring closure to afford a densely functionalized imidazo[1,2‐<em>a</em>]pyridine through formation of three C─N bonds.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 11","pages":"Article e70175"},"PeriodicalIF":2.7,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145501045","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}
Jingmin Chen , Yangyang Li , Jia Li , Jie Tao , Xudong Zhou , Wei Wang , Wenbing Sheng
Sulfonimidamides (SIAs) have garnered broad interests from medicinal chemists owing to their diverse and broad spectrum biological activities. This class of organosulfur compounds has also demonstrated promising applications in agriculture and materials science. In order to obtain structurally diverse SIAs and their N‐functionalized derivatives, a variety of synthetic methodologies have been developed. This review highlights the key discoveries and recent advances in this dynamic and rapidly evolving research field over the past decade. The synthetic approaches for SIAs include conventional synthetic methods, photocatalytic synthesis, transition metal‐catalyzed reactions, mechanochemical strategies, and SuFEx chemistry. Meanwhile, the N‐functionalization reactions encompass N‐aliphatic alkylation, N‐acylation, N‐arylation, and N‐sulfenylation. The challenges of N‐functionalization and outlooks on the application of SIAs are also concluded in this review.
{"title":"Recent Advances in the Synthesis and N‐Functionalization of Sulfonimidamides","authors":"Jingmin Chen , Yangyang Li , Jia Li , Jie Tao , Xudong Zhou , Wei Wang , Wenbing Sheng","doi":"10.1002/ajoc.202500535","DOIUrl":"10.1002/ajoc.202500535","url":null,"abstract":"<div><div>Sulfonimidamides (SIAs) have garnered broad interests from medicinal chemists owing to their diverse and broad spectrum biological activities. This class of organosulfur compounds has also demonstrated promising applications in agriculture and materials science. In order to obtain structurally diverse SIAs and their <em>N</em>‐functionalized derivatives, a variety of synthetic methodologies have been developed. This review highlights the key discoveries and recent advances in this dynamic and rapidly evolving research field over the past decade. The synthetic approaches for SIAs include conventional synthetic methods, photocatalytic synthesis, transition metal‐catalyzed reactions, mechanochemical strategies, and SuFEx chemistry. Meanwhile, the <em>N</em>‐functionalization reactions encompass <em>N‐</em>aliphatic alkylation, <em>N</em>‐acylation, <em>N</em>‐arylation, and <em>N</em>‐sulfenylation. The challenges of <em>N</em>‐functionalization and outlooks on the application of SIAs are also concluded in this review.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 11","pages":"Article e00535"},"PeriodicalIF":2.7,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145500892","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}
Naohiro Namba , Prof. Dr. Norimitsu Tohnai , Prof. Dr. Satoshi Minakata , Prof. Dr. Youhei Takeda
We report the synthesis of a new class of dibromodibenzo[a,j]phenazine (DBPHZ) derivatives bearing diaryl substituents at the 6,8–positions. These compounds were obtained through a combination of regioselective Pd‐catalyzed C─H direct arylation and oxidative skeletal rearrangement of appropriately functionalized binaphthalenediamines. The compatibility of bromine substituents with the C─H arylation conditions was confirmed, enabling the incorporation of various aryl groups including diphenyl, tert‐butylphenyl, and 3,5‐dimethylphenyl moieties. Crystallographic analysis of a representative compound revealed that the diaryl units adopt a twisted geometry relative to the DBPHZ core. Solubility tests demonstrated that the introduction of diaryl substituents having alkyl groups significantly enhances solubility in common organic solvents such as toluene and chloroform, compared to unsubstituted DBPHZ. Owing to the retained dibromo functionality, the synthesized DBPHZs would serve as valuable synthetic building blocks for constructing π‐extended functional organic materials.
{"title":"Synthesis of Solubility‐Enhanced 6,8‐Diarylated Dibromodibenzo[a,j]Phenazines via Pd‐Catalyzed C─H Arylation and Skeletal Rearrangement","authors":"Naohiro Namba , Prof. Dr. Norimitsu Tohnai , Prof. Dr. Satoshi Minakata , Prof. Dr. Youhei Takeda","doi":"10.1002/ajoc.70211","DOIUrl":"10.1002/ajoc.70211","url":null,"abstract":"<div><div>We report the synthesis of a new class of dibromodibenzo[<em>a,j</em>]phenazine (DBPHZ) derivatives bearing diaryl substituents at the 6,8–positions. These compounds were obtained through a combination of regioselective Pd‐catalyzed C─H direct arylation and oxidative skeletal rearrangement of appropriately functionalized binaphthalenediamines. The compatibility of bromine substituents with the C─H arylation conditions was confirmed, enabling the incorporation of various aryl groups including diphenyl, <em>tert</em>‐butylphenyl, and 3,5‐dimethylphenyl moieties. Crystallographic analysis of a representative compound revealed that the diaryl units adopt a twisted geometry relative to the DBPHZ core. Solubility tests demonstrated that the introduction of diaryl substituents having alkyl groups significantly enhances solubility in common organic solvents such as toluene and chloroform, compared to unsubstituted DBPHZ. Owing to the retained dibromo functionality, the synthesized DBPHZs would serve as valuable synthetic building blocks for constructing <em>π</em>‐extended functional organic materials.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 11","pages":"Article e70211"},"PeriodicalIF":2.7,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145500798","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}
Dr. Vianney Durel , Myriam Le Roch , Dr. Jacques Renault , Vincent Dorcet , Dr. Thierry Roisnel , Nicolas Gouault , Dr. Gilles Argouarch , Dr. Claudia Lalli
Peptidomimetics, that can take advantage of bioavailability and metabolic stability, are considered as an important class of molecules and constitute thus a large research field in medicinal chemistry. With the aim of obtaining constrained examples for drug discovery, we designed a two‐step synthesis of cis‐4‐hydroxy pipecolic acid derivatives as pseudodipeptides mimics. This straightforward procedure concerns the coupling of amino acid‐derived homoallylic amines with glyoxylic acid via an aza‐Prins cyclization to deliver piperidine‐lactones, followed by LiNTf2‐promoted aminolysis of the lactone with various amino acids. The 4‐hydroxy pipecolic acid peptidomimetics are obtained as single enantiomers and with a high diastereomeric control and they represent original and modular scaffolds for drug discovery.
{"title":"A Straightforward Access to Enantiopure 4‐Hydroxy‐pipecolic Acid Peptidomimetics by aza‐Prins Cyclization/LiNTf2‐Promoted Aminolysis of Lactones","authors":"Dr. Vianney Durel , Myriam Le Roch , Dr. Jacques Renault , Vincent Dorcet , Dr. Thierry Roisnel , Nicolas Gouault , Dr. Gilles Argouarch , Dr. Claudia Lalli","doi":"10.1002/ajoc.202500598","DOIUrl":"10.1002/ajoc.202500598","url":null,"abstract":"<div><div>Peptidomimetics, that can take advantage of bioavailability and metabolic stability, are considered as an important class of molecules and constitute thus a large research field in medicinal chemistry. With the aim of obtaining constrained examples for drug discovery, we designed a two‐step synthesis of cis‐4‐hydroxy pipecolic acid derivatives as pseudodipeptides mimics. This straightforward procedure concerns the coupling of amino acid‐derived homoallylic amines with glyoxylic acid via an aza‐Prins cyclization to deliver piperidine‐lactones, followed by LiNTf<sub>2</sub>‐promoted aminolysis of the lactone with various amino acids. The 4‐hydroxy pipecolic acid peptidomimetics are obtained as single enantiomers and with a high diastereomeric control and they represent original and modular scaffolds for drug discovery.\u0000</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 11","pages":"Article e00598"},"PeriodicalIF":2.7,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145500888","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}
Thiourea‐based organocatalysts have emerged as a cornerstone in asymmetric synthesis, offering powerful activation modes via dual hydrogen bonding while operating under mild, metal‐free conditions. This review provides a comprehensive overview of recent advances in thiourea‐amine catalysis in the last five years, highlighting its mechanistic foundations, structural innovations, and expanding functional scope. We first examine computational and experimental insights that have refined the mechanistic understanding of nucleophile and electrophile activation, with emphasis on noncovalent interactions, transition state engineering, and microenvironment effects. Next, we explore the evolution of catalyst architectures, including developments from natural chiral pool scaffolds, modular frameworks for dual activation, and multifunctional designs enabling remote or cooperative reactivity. We also detail recent integrations of thiourea catalysis with photoredox systems, chemoenzymatic cascades, and hybrid metal‐organic platforms, which have enabled new reactivity profiles and stereocontrol mechanisms. Most notably, we discuss the growing application of thiourea catalysts in polymer chemistry and CO2 conversion, including sequence‐controlled copolymerizations, degradable polyesters, and stimuli‐responsive systems for sustainable materials development. Through critical evaluation of these interdisciplinary advancements, this review outlines current challenges and future directions for thiourea‐amine catalysis, emphasizing its continued evolution as a versatile and sustainable tool in contemporary synthetic chemistry.
{"title":"Thiourea‐Amine Catalysts: Innovation, Integration, and Sustainability","authors":"Honghua Zhang , Yujun Qiao , Haile Chen , Yinliang Bai","doi":"10.1002/ajoc.202500582","DOIUrl":"10.1002/ajoc.202500582","url":null,"abstract":"<div><div>Thiourea‐based organocatalysts have emerged as a cornerstone in asymmetric synthesis, offering powerful activation modes via dual hydrogen bonding while operating under mild, metal‐free conditions. This review provides a comprehensive overview of recent advances in thiourea‐amine catalysis in the last five years, highlighting its mechanistic foundations, structural innovations, and expanding functional scope. We first examine computational and experimental insights that have refined the mechanistic understanding of nucleophile and electrophile activation, with emphasis on noncovalent interactions, transition state engineering, and microenvironment effects. Next, we explore the evolution of catalyst architectures, including developments from natural chiral pool scaffolds, modular frameworks for dual activation, and multifunctional designs enabling remote or cooperative reactivity. We also detail recent integrations of thiourea catalysis with photoredox systems, chemoenzymatic cascades, and hybrid metal‐organic platforms, which have enabled new reactivity profiles and stereocontrol mechanisms. Most notably, we discuss the growing application of thiourea catalysts in polymer chemistry and CO<sub>2</sub> conversion, including sequence‐controlled copolymerizations, degradable polyesters, and stimuli‐responsive systems for sustainable materials development. Through critical evaluation of these interdisciplinary advancements, this review outlines current challenges and future directions for thiourea‐amine catalysis, emphasizing its continued evolution as a versatile and sustainable tool in contemporary synthetic chemistry.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 11","pages":"Article e00582"},"PeriodicalIF":2.7,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145500970","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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