Zixuan Liu , Chenming Wang , Zhongyi Zhang , Xinyuan Lu , Ying Chen , Lijun Xu , Qing Huang , Wenyi Yuan
{"title":"Sustainable Electrocatalytic Strategy for C─CF2 Bond Construction via Decarboxylative Difluoroalkylation","authors":"Zixuan Liu , Chenming Wang , Zhongyi Zhang , Xinyuan Lu , Ying Chen , Lijun Xu , Qing Huang , Wenyi Yuan","doi":"10.1002/ajoc.70402","DOIUrl":"10.1002/ajoc.70402","url":null,"abstract":"<div><div>We disclose an electrocatalytic strategy for constructing C─CF<sub>2</sub> bonds by using inexpensive and commercially available ethyl bromodifluoroacetate (BrCF<sub>2</sub>CO<sub>2</sub>Et) as a difluoroalkylating reagent. This method enables the efficient difluoroalkylation of a range of unsaturated substrates, including cinnamic acids, alkenes, and indoles. The reactions are carried out in a membrane‐free electrolytic cell without the need for precious metal catalysts, demonstrating excellent functional group compatibility and broad substrate scope. Through systematic optimization of critical parameters such as electrode materials, electrolytes, and current density, optimal conditions were established, achieving yields of up to 82% for cinnamic acid derivatives. Moreover, the strategy is successfully applied to downstream derivatizations, offering a promising and versatile approach for the synthesis of high‐value fluorinated molecules. Possible reaction mechanism suggested the involvement of a ferrocene‐mediated radical/redox process.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 4","pages":"Article e70402"},"PeriodicalIF":2.7,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147753662","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}
Kamal Kant , Dhananjaya Kaldhi , Ahanthem Sonia , Thounaojam A. Devi , Jyoti , Arup K. Kabi , Virender Singh , Chandi C. Malakar , Reda A. Haggam
{"title":"Conversion of Organic Amines Into Organic Iodides and Simple Arenes via Metal‐Free Direct Deamination Approach","authors":"Kamal Kant , Dhananjaya Kaldhi , Ahanthem Sonia , Thounaojam A. Devi , Jyoti , Arup K. Kabi , Virender Singh , Chandi C. Malakar , Reda A. Haggam","doi":"10.1002/ajoc.70396","DOIUrl":"10.1002/ajoc.70396","url":null,"abstract":"<div><div>We present a unified and operationally straightforward strategy for the direct synthesis of iodoarenes, iodoalkanes, and arene derivatives under nitrite‐free conditions. This dual catalytic platform encompasses two mechanistically distinct pathways: (i) a potassium iodide‐catalyzed deamination protocol involving the in situ generation of nitrous acid from hydroxylamine hydrochloride and <em>tert</em>‐butyl hydroperoxide (TBHP), mediated by iodine (I<sub>2</sub>), which facilitates diazotization of primary amines followed by C─X bond formation to furnish iodoarenes and iodoalkanes; and (ii) a silane‐mediated deamination pathway that bypasses conventional diazonium intermediates, enabling reductive deamination to access arenes. Both approaches eliminate the need for traditional nitrite salts, offering a metal‐efficient and environmentally benign alternative. The methodology demonstrates broad substrate scope across aromatic and aliphatic amines, affording structurally diverse deaminated products in yields of up to 95%. By avoiding reliance on hazardous nitrite‐based reagents, this work provides a sustainable and versatile platform for the synthesis of valuable iodoarene, iodoalkane, and arene scaffolds with wide synthetic applicability.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 4","pages":"Article e70396"},"PeriodicalIF":2.7,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147668561","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}
Manuel A. Rentería‐Gómez , Diana García‐García , Alejandro Corona‐Díaz , Rocío Gámez‐Montaño
{"title":"Green Multicomponent‐Click Strategy for One‐Pot Synthesis of Polyheterocyclic Estazolam Aza‐Analogs and Their Symmetrical Polyheterocycles","authors":"Manuel A. Rentería‐Gómez , Diana García‐García , Alejandro Corona‐Díaz , Rocío Gámez‐Montaño","doi":"10.1002/ajoc.70382","DOIUrl":"10.1002/ajoc.70382","url":null,"abstract":"<div><div>A novel one‐pot synthesis of polyheterocyclic compounds (PHCs) incorporating fused 1,5‐disubstituted 1,2,3‐triazole‐1,4‐benzodiazepines (fused 1,5‐Ds‐1,2,3‐T‐1,4‐BZD) bound to 1,5‐disubstituted tetrazoles (1,5‐Ds‐Ts) was developed via Ugi‐azide four‐component reaction (UA‐4CR), followed by an intramolecular alkyne–azide cycloaddition (IAAC). The strategy features overall yields up to 92%, the construction of three heterocycles, broad applicability to UA‐4CR products, a single purification step via flash column chromatography, green solvent conditions (water or EtOH), and scalability. The secondary amine functional group in PHCs enabled further structural diversification in the synthesis of symmetrical polyheterocycles (SPHs) and structurally aza‐analogs of estazolam. This is the first report of an alternative energy sources (AES)‐assisted UA‐4CR/IAAC strategy for the synthesis of fused 1,5‐Ds‐1,2,3‐T‐1,4‐BZD, applied to the synthesis of SPHs that allow the construction of six heterocyclic rings.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 4","pages":"Article e70382"},"PeriodicalIF":2.7,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147668106","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}
Alexey R. Romanov , Vyacheslav V. Filatov , Sergey V. Zinchenko , Stepan A. Ukhanev
{"title":"Synthesis of 5‐Trifluoromethyl‐4,5‐dihydrooxazoles From Trifluoromethyl(alkenyl)ketones and p‐Tosylmethylisocyanide","authors":"Alexey R. Romanov , Vyacheslav V. Filatov , Sergey V. Zinchenko , Stepan A. Ukhanev","doi":"10.1002/ajoc.70393","DOIUrl":"10.1002/ajoc.70393","url":null,"abstract":"<div><div>A simple synthetic approach towards 5‐(trifluoromethyl)‐4,5‐dihydrooxazoles was elaborated. To this end, the reaction of trifluoromethyl(alkenyl)ketones with <em>p</em>‐tosylmethylisocyanide (TosMIC) in the presence of the base was employed to afford the target heterocycles in good to high yields. The process is characterized by high stereo‐ and chemoselectivity. The stereochemistry of the 4,5‐dihydrooxazoles is unambiguously proved by the combination of NMR and quantum chemical calculational methods. The formation of the oxazole cycle occurs via nucleophilic attack of TosMIC on the carbonyl moiety, followed by intramolecular cyclization with participation of the isocyanide fragment.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 4","pages":"Article e70393"},"PeriodicalIF":2.7,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147668372","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}
{"title":"Photochemical Reductive Regeneration of Benzimidazoline Accelerated by OH or NH Bonds Adjacent to the Reaction Center","authors":"Tatsuhiro Harada , Suguru Murakami , Masahiko Hayashi , Ryosuke Matsubara","doi":"10.1002/ajoc.70420","DOIUrl":"10.1002/ajoc.70420","url":null,"abstract":"<div><div>1,3‐Dimethylbenzimidazoline (BIH) is an organic hydride with a strong hydride‐donating capacity. Photochemical regeneration of BIH derivatives from their oxidized form, 1,3‐benzimidazolium, using inexpensive reductants is crucial for their practical application as catalysts. We observed that 2‐aryl‐BIH compounds, bearing a heteroatom–hydrogen bond at the ortho‐position of the phenyl substituent attached to the C2 position of the benzimidazoline ring, underwent rapid regeneration by ascorbate under visible‐light irradiation. Computational analyses revealed that the heteroatom–hydrogen bond facilitated BIH regeneration by forming a hydrogen bond with ascorbate and/or by mediating inter‐ and intramolecular transfer of a proton and an electron. This paper presents an environmentally sustainable strategy for utilizing BIH‐based systems as reductive catalysts.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 4","pages":"Article e70420"},"PeriodicalIF":2.7,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147753664","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}
Meng‐Hsia Tsai , Yu‐Jin Huang , Xsingyi Lee , Cheng‐Kun Lin
{"title":"In Situ Generation of tert‐Butyl Carbonate From Boc2O Enables Synthesis of Cyclic Carbonates Under Mild Conditions","authors":"Meng‐Hsia Tsai , Yu‐Jin Huang , Xsingyi Lee , Cheng‐Kun Lin","doi":"10.1002/ajoc.70413","DOIUrl":"10.1002/ajoc.70413","url":null,"abstract":"<div><div>A mild and efficient one‐pot strategy for synthesizing five‐membered cyclic carbonates has been developed using Boc<sub>2</sub>O as a carbon dioxide surrogate. This transformation proceeds under ambient conditions without metal catalysts, tolerating a wide range of aryl, alkyl, and heteroatom‐substituted epoxides. The studies reveal that <em>tert</em>‐butyl carbonate, formed in situ from Boc<sub>2</sub>O and amines, undergoes nucleophilic epoxide ring opening followed by intramolecular acyl substitution. The addition of TBAB significantly enhances reactivity, likely by stabilizing ionic intermediates. The protocol affords good to excellent yields (up to 99%) and maintains high enantiopurity for chiral substrates. This operationally simple and scalable method provides an attractive alternative to traditional CO<sub>2</sub> fixation routes and demonstrates the synthetic utility of Boc<sub>2</sub>O beyond its conventional role as a protecting agent.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 4","pages":"Article e70413"},"PeriodicalIF":2.7,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147753741","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}
Alageswaran Jayaram , Vijay Thavasianandam Seenivasan , Yu‐Ming Liu , Yu‐Chen Lin , Tsz‐Fai Leung , Ching‐Ching Yu , Wei‐Yu Lin
{"title":"CBr4‐Mediated Metal‐Free Sulfonamide Synthesis: A Comparative Study Under Batch, Continuous‐Flow and Ultrasonic Conditions","authors":"Alageswaran Jayaram , Vijay Thavasianandam Seenivasan , Yu‐Ming Liu , Yu‐Chen Lin , Tsz‐Fai Leung , Ching‐Ching Yu , Wei‐Yu Lin","doi":"10.1002/ajoc.70384","DOIUrl":"10.1002/ajoc.70384","url":null,"abstract":"<div><div>Sulfonamides are vital scaffolds in pharmaceuticals and materials chemistry. While most oxidative sulfonamide syntheses predominantly relied iodine‐mediated protocols, bromine‐based systems remain largely unexplored. In this study, we report a CBr<sub>4</sub>‐mediated oxidative coupling of sodium benzenesulfinamide with diverse primary and secondary amines under metal‐free conditions, offering an efficient and sustainable alternative to conventional approaches. The reaction proceeds smoothly under mild conditions, affording a broad range of sulfonamides in high yields with excellent functional group compatibility. Furthermore, comparative studies under batch, continuous‐flow, and ultrasound‐assisted conditions revealed that the continuous‐flow process remarkably reduced reaction time from 4 h to 15.7 min while eliminating the need for external heating and maintaining superior yields. This work not only provides a practical and efficient route to sulfonamides but also fills a significant methodological gap in halogen‐mediated oxidative coupling chemistry.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 4","pages":"Article e70384"},"PeriodicalIF":2.7,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147668506","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}
Prakash K. Mandal , Ramlal Baidya , Sourav Pakrashy , Anindya S. Manna , Tanmay K. Pati , Dilip K. Maiti
{"title":"Organocatalyzed Sustainable Annulation to Construct 4‐Amino‐ and 4‐Thioquinoline Scaffolds as Potential Cancer Therapeutics","authors":"Prakash K. Mandal , Ramlal Baidya , Sourav Pakrashy , Anindya S. Manna , Tanmay K. Pati , Dilip K. Maiti","doi":"10.1002/ajoc.70371","DOIUrl":"10.1002/ajoc.70371","url":null,"abstract":"<div><div>An inventive and versatile one‐pot, atom‐economical, inexpensive organocatalyzed sustainable annulation strategy has been developed for the synthesis of bioactive 4‐arylamino/arylthio‐2,3‐substituted quinolines with excellent pharmaceutical potential as a candidate for anticancer activity, according to the outcome of performed molecular docking studies. This novel, metal‐free, eco‐benign, domino, multicomponent annulation protocol facilitates simultaneous C═N, C─C, C═C, and C─N/C─S bond formation utilizing an organic Brønsted acid catalyst, <em>p</em>‐TSA.H<sub>2</sub>O. The reaction protocol proceeds through a benign and efficient pathway under both conventional heating and microwave irradiation conditions. Furthermore, prolific and diverse substrate scopes were explored through this methodology, including drug‐like architectures involving various nucleophiles such as 2‐alkynylanilines, thiophenols, aromatic amine, alkyl amine, amide, sulfonamide, and so forth. Herein, we have also established the proposed plausible mechanistic hypothesis through the relevant control experiments, prevailing literature supports, and HRMS kinetic study outcome.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 4","pages":"Article e70371"},"PeriodicalIF":2.7,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147668107","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}
Denis N. Tomilin , Sophia A. Stepanova , Tatyana N. Borodina , Igor A. Ushakov
{"title":"3‐Acetylpyrrolo[1,2‐c]Oxazoles, Bipyrrolo[1,2‐c]Oxazoles, and Pyrrolo[1,2‐c]Oxazole‐Oxetane Ensembles via Base‐Catalyzed [3 + 2]‐Cyclization of 2‐Acylethynylpyrroles With Diacetyl","authors":"Denis N. Tomilin , Sophia A. Stepanova , Tatyana N. Borodina , Igor A. Ushakov","doi":"10.1002/ajoc.70381","DOIUrl":"10.1002/ajoc.70381","url":null,"abstract":"<div><div>A stereoselective, base‐catalyzed [3 + 2]‐cyclization of 2‐acylethynylpyrroles with diacetyl (DBU/benzene, room temperature) afforded bipyrrolo[1,2‐<em>c</em>]oxazoles or 3‐acetylpyrrolo[1,2‐<em>c</em>]oxazoles, both integrated with <em>α,β</em>‐ethylenic ketones, in 51–76% and 23–74% yields, respectively. Switching between these products was controlled by the concentration of diacetyl. Replacing the catalyst with NaOH triggered an unexpected Paternò–Büchi dimerization of diacetyl, followed by a [3 + 2]‐cyclization to yield pyrrolo[1,2‐<em>c</em>]oxazole‐oxetane ensembles (21–29%) alongside the aforementioned pyrrolo‐ and bipyrrolo[1,2‐<em>c</em>]oxazoles.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 4","pages":"Article e70381"},"PeriodicalIF":2.7,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147668871","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}
{"title":"Phenanthroline‐Mediated, Metal‐ and Photocatalyst‐Free Visible‐Light Synthesis of Quinazolin‐4(3H)‐ones From 2‐Amidoaryl Oxazolines for Rapid‐Readout System Applications","authors":"Weiqiang Chen , Hao Long","doi":"10.1002/ajoc.70388","DOIUrl":"10.1002/ajoc.70388","url":null,"abstract":"<div><div>A novel, metal‐ and photocatalyst‐free strategy has been developed for the visible‐light synthesis of quinazolin‐4(3H)‐ones from 2‐amidoaryl oxazolines, with phenanthroline serving as a crucial promoter. The strategy highlights the potential of using readily available organic molecules to construct complex heterocycles under mild conditions. This approach offers a sustainable and operationally simple protocol, avoiding the need for costly metals or specialized photoactive catalysts. Importantly, the resulting quinazolin‐4(3<em>H</em>)‐ones have been successfully applied in a rapid‐readout system, demonstrating their utility for fast and convenient detection.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 4","pages":"Article e70388"},"PeriodicalIF":2.7,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147686142","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}