Asian Journal of Organic Chemistry最新文献

{"title":"The Evolved Synthetic Strategy to (+)‐Isostrychnine","authors":"Weigang He, Pengyan Wang, Junhan Chen, Qianhu Chen, Huanhuan Zou, Jiahang Yan, Jiangang Gan, Weiqing Xie","doi":"10.1002/ajoc.70522","DOIUrl":"10.1002/ajoc.70522","url":null,"abstract":"<div><div>The intriguing structure of strychnine has continuously inspired the development of novel strategies and methodologies in organic synthesis. We have established a general synthetic platform for constructing the octahydro‐1H‐pyrrolo[2,3‐<em>d</em>]carbazole scaffold (A–B–C–E rings) via a sequential catalytic tandem double Michael addition/cyclization process, which enables the collective synthesis of monoterpenoid indole alkaloids. Herein, we detail our evolved strategy toward (+)‐isostrychnine—a key precursor for strychnine synthesis—based on this platform. The total synthesis of (+)‐isostrychnine is characterized by an intramolecular cascade condensation/lactamization reaction, which efficiently constructs both the E‐ and G‐rings in one pot from an enantioenriched spirooxindole synthon. Although the formation of the D‐ring via intramolecular allylic nucleophilic addition of propargyl silane to allylic alcohol was successfully achieved under SnCl<sub>4</sub> promotion, the elaboration of the resulting allene intermediate proved unsuccessful. Eventually, by leveraging an allylic diazene rearrangement followed by an intramolecular Heck reaction, the bridged D‐ring was successfully constructed, culminating in the total synthesis of (+)‐isostrychnine in nine longest linear steps (LLS) with an overall yield of 16%.</div></div><div>The intriguing structure of strychnine has continuously inspired the development of novel strategies and methodologies in organic synthesis. We have established a general synthetic platform for constructing the octahydro‐1H‐pyrrolo[2,3‐<em>d</em>]carbazole scaffold (A–B–C–E rings) via a sequential catalytic tandem double Michael addition/cyclization process, which enables the collective synthesis of monoterpenoid indole alkaloids. Herein, we detail our evolved strategy toward (+)‐isostrychnine—a key precursor for strychnine synthesis—based on this platform. The total synthesis of (+)‐isostrychnine is characterized by an intramolecular cascade condensation/lactamization reaction, which efficiently constructs both the E‐ and G‐rings in one pot from an enantioenriched spirooxindole synthon. Although the formation of the D‐ring via intramolecular allylic nucleophilic addition of propargyl silane to allylic alcohol was successfully achieved under SnCl<sub>4</sub> promotion, the elaboration of the resulting allene intermediate proved unsuccessful. Eventually, by leveraging an allylic diazene rearrangement followed by an intramolecular Heck reaction, the bridged D‐ring was successfully constructed, culminating in the total synthesis of (+)‐isostrychnine in nine longest linear steps (LLS) with an overall yield of 16%.</div><div>Total synthesis of (+)‐isostrychnine was accomplished in nine longest linear steps enabled by catalytic asymmetric tandem double Michael addition, which featured an intramolecular condensation/lactamization to forge the F/G rings, and an allylic diazene rearrangement/intramolecular Heck sequence to ","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 8","pages":"Article e70522"},"PeriodicalIF":2.3,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148952592","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":"Quinoline‐Based Fluorescent Probes for H2O2 Detection: Optimizing Performance with Electron‐Donating Groups at the 7‐Position","authors":"Xing Peng, Jingru Xiao, Beibei Qin, Mingyang Huang, Saffar Andaloussi Rim, Liang Jiang, Xiao Yun Chen","doi":"10.1002/ajoc.70533","DOIUrl":"10.1002/ajoc.70533","url":null,"abstract":"<div><div>The fluorescent probes based on quinoline have garnered lots of attention due to their excellent photophysical properties. Normally the electron‐rich group connected at 7‐position of quinoline can form a better ICT effect in the conjugation which can enhance the photoluminescence properties of probes. To evaluate the role of these electron‐donating groups in probe performance, we designed, calculated and prepared three probes based on electron‐rich oxystyrylquinoline based on the results of theoretical calculations, featuring distinct substituents (<strong>QTD</strong>, <strong>QTM</strong>, and <strong>QTH</strong>) and investigated their structure–property relationships. Theoretical calculations show that <strong>QTM</strong> owns the strongest oscillator strength (0.6477) and the narrowest energy gap (2.8390 eV) among the three probes, which is consistent with its distinct ICT effect. Due to diminished electron‐donating strength, probe <strong>QTM</strong> emits in the red region (646 nm), while <strong>QTH</strong> and <strong>QTD</strong> showed blue shifted emissions at 618 and 554 nm, respectively. The studies of photophysical and sensing properties confirmed that stronger electron‐donation enhances ICT effect, resulting in longer emission wavelengths. <strong>QTM</strong> achieved the best property, with a detection limit of 32.32 µM, 180 min response time, and 79.32% quenching efficiency. An integrated computational/experimental approach was used to synergize theoretical calculation with experimental validation.</div></div><div>The fluorescent probes based on quinoline have garnered lots of attention due to their excellent photophysical properties. Normally the electron‐rich group connected at 7‐position of quinoline can form a better ICT effect in the conjugation which can enhance the photoluminescence properties of probes. To evaluate the role of these electron‐donating groups in probe performance, we designed, calculated and prepared three probes based on electron‐rich oxystyrylquinoline based on the results of theoretical calculations, featuring distinct substituents (<strong>QTD</strong>, <strong>QTM</strong>, and <strong>QTH</strong>) and investigated their structure–property relationships. Theoretical calculations show that <strong>QTM</strong> owns the strongest oscillator strength (0.6477) and the narrowest energy gap (2.8390 eV) among the three probes, which is consistent with its distinct ICT effect. Due to diminished electron‐donating strength, probe <strong>QTM</strong> emits in the red region (646 nm), while <strong>QTH</strong> and <strong>QTD</strong> showed blue shifted emissions at 618 and 554 nm, respectively. The studies of photophysical and sensing properties confirmed that stronger electron‐donation enhances ICT effect, resulting in longer emission wavelengths. <strong>QTM</strong> achieved the best property, with a detection limit of 32.32 µM, 180 min response time, and 79.32% quenching efficiency. An int","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 8","pages":"Article e70533"},"PeriodicalIF":2.3,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148952598","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":"Unexpected Sodium Bicarbonate‐promoted P–S Coupling of N‐sulfonylhydrazones with Diarylphosphine Oxides to Afford Phosphorothioates","authors":"Jiawei Liu,&nbsp;Shaoqing Liu,&nbsp;Li‐Biao Han,&nbsp;Ruwei Shen","doi":"10.1002/ajoc.70528","DOIUrl":"10.1002/ajoc.70528","url":null,"abstract":"<div><div>An unprecedented P–S coupling of trifluoroacetophenone <em>N</em>‐sulfonylhydrazones with diarylphosphine oxides is described to afford phosphorothioates with high selectivity. In contrast to the conventional use of <em>N</em>‐sulfonylhydrazones as diazo precursors, trifluoroacetophenone‐derived <em>N</em>‐sulfonylhydrazones formally transfers a RS moiety in the reaction. The reaction scope was examined and a plausible mechanism proposed based on control experiments.</div></div><div>An unprecedented P–S coupling of trifluoroacetophenone <em>N</em>‐sulfonylhydrazones with diarylphosphine oxides is described to afford phosphorothioates with high selectivity. In contrast to the conventional use of <em>N</em>‐sulfonylhydrazones as diazo precursors, trifluoroacetophenone‐derived <em>N</em>‐sulfonylhydrazones formally transfers a RS moiety in the reaction. The reaction scope was examined and a plausible mechanism proposed based on control experiments.</div><div>An unexpected P–S coupling of trifluoroacetophenone N‐sulfonylhydrazones with diarylphosphine oxides is described, affording phosphorothioates with high selectivity.\u0000<span><figure><span><img><ol><li><span><span>Download: <span>Download high-res image (13KB)</span></span></span></li><li><span><span>Download: <span>Download full-size image</span></span></span></li></ol></span></figure></span></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 8","pages":"Article e70528"},"PeriodicalIF":2.3,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148952661","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":"Metal‐Free TBN‐Mediated Regioselective Azolation of Phenols","authors":"Yongliang Pan,&nbsp;Xianbo Huang,&nbsp;Liyuan Hou,&nbsp;Ling Lin,&nbsp;Yu Tang,&nbsp;Pengju Feng","doi":"10.1002/ajoc.70510","DOIUrl":"10.1002/ajoc.70510","url":null,"abstract":"<div><div>A metal‐free, ortho‐selective C–H amination of phenols with azoles using TBN as the sole mediator is reported. The reaction provides direct access to N‐arylazoles, key scaffolds in pharmaceuticals and agrochemicals, under mild conditions (room temperature, inert atmosphere) without transition‐metal catalysts, prefunctionalized arenes, or external oxidants. A wide range of phenols and azoles (pyrazoles, imidazoles, triazoles, and tetrazoles) are compatible, affording ortho‐aminated products in good to excellent yields (up to 94%) with exceptional regiocontrol. Gram‐scale synthesis (2.08 g, 77% yield) and subsequent derivatizations demonstrate synthetic utility. Mechanistic studies support a radical pathway involving TBN‐generated nitrogen‐centered radicals.</div></div><div>A metal‐free, ortho‐selective C–H amination of phenols with azoles using TBN as the sole mediator is reported. The reaction provides direct access to N‐arylazoles, key scaffolds in pharmaceuticals and agrochemicals, under mild conditions (room temperature, inert atmosphere) without transition‐metal catalysts, prefunctionalized arenes, or external oxidants. A wide range of phenols and azoles (pyrazoles, imidazoles, triazoles, and tetrazoles) are compatible, affording ortho‐aminated products in good to excellent yields (up to 94%) with exceptional regiocontrol. Gram‐scale synthesis (2.08 g, 77% yield) and subsequent derivatizations demonstrate synthetic utility. Mechanistic studies support a radical pathway involving TBN‐generated nitrogen‐centered radicals.</div><div>A metal‐free, TBN‐mediated ortho‐selective C–H amination of phenols with azoles enables direct access to diverse N‐arylazoles under mild conditions with broad substrate scope and excellent regiocontrol.\u0000<span><figure><span><img><ol><li><span><span>Download: <span>Download high-res image (26KB)</span></span></span></li><li><span><span>Download: <span>Download full-size image</span></span></span></li></ol></span></figure></span></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 8","pages":"Article e70510"},"PeriodicalIF":2.3,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148752632","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":"Rh‐Catalyzed [5+2] Annulation of Aryl Oximes With Maleimides to Access Azepino[3,2‐b]indoles","authors":"Yueji Luo,&nbsp;Boen Mao,&nbsp;Cheng Ye,&nbsp;Jieni Lei,&nbsp;Yaqian Li,&nbsp;Zi Yang","doi":"10.1002/ajoc.70514","DOIUrl":"10.1002/ajoc.70514","url":null,"abstract":"<div><div>Azepino[3,2‐<em>b</em>]indoles are a class of pharmaceutically significant molecules containing an aza‐seven‐membered ring system. However, synthetic approaches to this scaffold remain limited and typically require multiple steps. Herein, we demonstrate the feasibility of synthesizing azepino[3,2‐<em>b]</em>indoles via a Rh(III)‐catalyzed C─H activation followed by an annulation process using readily available ayrl oximes and maleimides. Moreover, this methodology features a short reaction time and broad functional group compatibility.</div></div><div>Azepino[3,2‐<em>b</em>]indoles are a class of pharmaceutically significant molecules containing an aza‐seven‐membered ring system. However, synthetic approaches to this scaffold remain limited and typically require multiple steps. Herein, we demonstrate the feasibility of synthesizing azepino[3,2‐<em>b]</em>indoles via a Rh(III)‐catalyzed C─H activation followed by an annulation process using readily available ayrl oximes and maleimides. Moreover, this methodology features a short reaction time and broad functional group compatibility.</div><div>A novel protocol for synthesizing azepino[3,2‐b]indoles from readily available aryl oximes and maleimides through the Rhodium(III)‐catalyzed C─ Hbond activation and intramolecular annulation reaction has been described. This strategy features powerful reactivity, tolerates various functional groups, and proceeds with moderate yields under mild reaction conditions.\u0000<span><figure><span><img><ol><li><span><span>Download: <span>Download high-res image (19KB)</span></span></span></li><li><span><span>Download: <span>Download full-size image</span></span></span></li></ol></span></figure></span></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 8","pages":"Article e70514"},"PeriodicalIF":2.3,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148752874","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":"Photoinduced Borylation of Aryl Halides, Including Aryl Chlorides, Under Photocatalyst‐Free Conditions","authors":"Eiji Yamaguchi,&nbsp;Takuya Ikuta,&nbsp;Ramasamy Aragarsamy,&nbsp;Norihiro Tada,&nbsp;Satoshi Endo,&nbsp;Akichika Itoh","doi":"10.1002/ajoc.70498","DOIUrl":"10.1002/ajoc.70498","url":null,"abstract":"&lt;div&gt;&lt;div&gt;A photocatalyst‐free photoinduced borylation of activated aryl chlorides has been developed using a simple base/additive system. Under 365 nm LED irradiation, electron‐deficient aryl chlorides underwent borylation with bis(pinacolato)diboron in MeCN in the presence of aqueous TBAOH and CsF, affording arylboronates under transition‐metal‐free conditions. Optimization revealed that both base and fluoride additive are essential, with TBAOH/CsF effectively promoting activation of electron‐deficient aryl chlorides. The method tolerated activated aryl chlorides bearing electron‐withdrawing substituents, including cyano and amide groups, whereas electron‐neutral and electron‐rich substrates showed markedly lower reactivity. Aryl bromides and iodides also participated under related conditions, indicating strong dependence on the halogen substituent. Control experiments confirmed that light irradiation is required and that the reaction is not thermally initiated. Radical‐quenching and deuterium‐labeling experiments support aryl radical intermediates. Accordingly, a mechanism involving photoinduced single‐electron transfer to the aryl halide followed by C─X bond cleavage is proposed.&lt;/div&gt;&lt;/div&gt;&lt;div&gt;A photocatalyst‐free photoinduced borylation of activated aryl chlorides has been developed using a simple base/additive system. Under 365 nm LED irradiation, electron‐deficient aryl chlorides underwent borylation with bis(pinacolato)diboron in MeCN in the presence of aqueous TBAOH and CsF, affording arylboronates under transition‐metal‐free conditions. Optimization revealed that both base and fluoride additive are essential, with TBAOH/CsF effectively promoting activation of electron‐deficient aryl chlorides. The method tolerated activated aryl chlorides bearing electron‐withdrawing substituents, including cyano and amide groups, whereas electron‐neutral and electron‐rich substrates showed markedly lower reactivity. Aryl bromides and iodides also participated under related conditions, indicating strong dependence on the halogen substituent. Control experiments confirmed that light irradiation is required and that the reaction is not thermally initiated. Radical‐quenching and deuterium‐labeling experiments support aryl radical intermediates. Accordingly, a mechanism involving photoinduced single‐electron transfer to the aryl halide followed by C─X bond cleavage is proposed.&lt;/div&gt;&lt;div&gt;A simple combination of tetrabutylammonium hydroxide and cesium fluoride enables photocatalyst‐free borylation of aryl chlorides under 365 nm irradiation. Electron‐deficient aryl chlorides are converted into the corresponding arylboronates under metal‐free conditions, providing a practical strategy for photoinduced activation of otherwise challenging carbon–chlorine bonds.\u0000&lt;span&gt;&lt;figure&gt;&lt;span&gt;&lt;img&gt;&lt;ol&gt;&lt;li&gt;&lt;span&gt;&lt;span&gt;Download: &lt;span&gt;Download high-res image (9KB)&lt;/span&gt;&lt;/span&gt;&lt;/span&gt;&lt;/li&gt;&lt;li&gt;&lt;span&gt;&lt;span&gt;Download: &lt;span&gt;Download full-size image&lt;/span&gt;&lt;/span&gt;&lt;/span&gt;&lt;/li&gt;&lt;/ol","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 8","pages":"Article e70498"},"PeriodicalIF":2.3,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148647721","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":"Halogenation of (Hetero)Aryl Boronic Acids/Esters: Approaches, Mechanisms, and Selectivity","authors":"Zhilong Chen,&nbsp;Jiao Kang","doi":"10.1002/ajoc.70525","DOIUrl":"10.1002/ajoc.70525","url":null,"abstract":"<div><div>Hetero)aryl boronic acids/esters are extremely useful synthetic building blocks, serving as starting materials or key intermediates in preparation of many useful compounds. Halogenation of (hetero)aryl boronic acids/esters is a frequently used method to introduce halogens, particularly for selective late‐stage radiohalogenation of drug molecules/leads. Diverse products can be obtained under different conditions. Therefore, the chemo‐ and regioselectivities are worthy attention. In this review, we summarize recent developments in the halogenation of (hetero)aryl boronic acids, including transition metal (TM)‐mediated/catalyzed aromatic substitution (S_Ar) halogenation of boronic acids/esters, <em>ipso</em>‐halogenation, Ar‐H halogenation without modifying the boronic acid/ester moiety, and <em>ipso</em>‐hydroxylation–halogenation. These approaches not only expand the accessible chemical space of (hetero)aryl boronic acids/esters, but also serve as useful tools in related research. Mechanism and perspective were also discussed.</div></div><div>Hetero)aryl boronic acids/esters are extremely useful synthetic building blocks, serving as starting materials or key intermediates in preparation of many useful compounds. Halogenation of (hetero)aryl boronic acids/esters is a frequently used method to introduce halogens, particularly for selective late‐stage radiohalogenation of drug molecules/leads. Diverse products can be obtained under different conditions. Therefore, the chemo‐ and regioselectivities are worthy attention. In this review, we summarize recent developments in the halogenation of (hetero)aryl boronic acids, including transition metal (TM)‐mediated/catalyzed aromatic substitution (S_Ar) halogenation of boronic acids/esters, <em>ipso</em>‐halogenation, Ar‐H halogenation without modifying the boronic acid/ester moiety, and <em>ipso</em>‐hydroxylation–halogenation. These approaches not only expand the accessible chemical space of (hetero)aryl boronic acids/esters, but also serve as useful tools in related research. Mechanism and perspective were also discussed.</div><div>Halogenation of (hetero)aryl boronic acids/esters is frequently used to introduce halogens, particularly for selective late‐stage radio‐halogenation of drug molecules or leads, but diverse products can be obtained under different conditions. In this manuscript, we summarize recent developments in halogenation of (hetero)aryl boronic acids, including transition metal (TM)‐mediated/catalyzed halide aromatic substitution (S_Ar) of boronic acids/esters, <em>ipso</em>‐halogenation, Ar‐H halogenation without modifying the boronic acid/ester group, and <em>ipso</em>‐hydroxylation–halogenation.\u0000<span><figure><span><img><ol><li><span><span>Download: <span>Download high-res image (17KB)</span></span></span></li><li><span><span>Download: <span>Download full-size image</span></span></span></li></ol></span></figure></span></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 8","pages":"Article e70525"},"PeriodicalIF":2.3,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148952590","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":"Electrochemical Synthesis of Ketones","authors":"Xinyue Dong,&nbsp;Xiao‐Jin Sun,&nbsp;Yi‐Lin Wang,&nbsp;Can Zhang,&nbsp;Xiao‐Tian Wang,&nbsp;Xin‐Ran Shi,&nbsp;Zhan‐Yong Wang","doi":"10.1002/ajoc.70503","DOIUrl":"10.1002/ajoc.70503","url":null,"abstract":"<div><div>Ketones are important organic compounds. Electrosynthesis offers a mild and sustainable route for ketone synthesis. In this review, rather than summarizing reactions by substrate class or catalytic system, we adopt a mechanistically guided classification based on the origin of the carbonyl oxygen atom. Recent progress is accordingly divided into two categories: (1) transformations using non‐ketone oxygen sources (water, O₂, CO, CO₂, TEMPO, alcohols, acids, esters, and aldehydes). (2) functionalization of simple ketone‐containing molecules to access complex ketones. Organizing these methods according to oxygen source provides a unified mechanistic overview and practical guidance for reagent selection.</div></div><div>Ketones are important organic compounds. Electrosynthesis offers a mild and sustainable route for ketone synthesis. In this review, rather than summarizing reactions by substrate class or catalytic system, we adopt a mechanistically guided classification based on the origin of the carbonyl oxygen atom. Recent progress is accordingly divided into two categories: (1) transformations using non‐ketone oxygen sources (water, O₂, CO, CO₂, TEMPO, alcohols, acids, esters, and aldehydes). (2) functionalization of simple ketone‐containing molecules to access complex ketones. Organizing these methods according to oxygen source provides a unified mechanistic overview and practical guidance for reagent selection.</div><div>This review focuses on how electrochemistry enables the facile construction of ketones, along with the associated strategies and mechanisms. Recent advances have been summarized via two categories by sources carbonyl oxygen: (1) transformations using non‐ketone oxygen sources (water, O₂, CO, CO₂, TEMPO, alcohols, acids, esters, and aldehydes). (2) functionalization of simple ketone‐ containing molecules to access complex ketones.\u0000<span><figure><span><img><ol><li><span><span>Download: <span>Download high-res image (24KB)</span></span></span></li><li><span><span>Download: <span>Download full-size image</span></span></span></li></ol></span></figure></span></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 8","pages":"Article e70503"},"PeriodicalIF":2.3,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148752804","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":"Synergistic Catalytic Mechanism of Glutarimide Ionic Liquids in Atmospheric Pressure Cycloaddition of CO2 With Epichlorohydrin","authors":"Xin Wang,&nbsp;Bingxin Wang,&nbsp;Ruiyu Zhang,&nbsp;Huali Jia,&nbsp;Chenyi Cai,&nbsp;Zichen Zhao,&nbsp;Xiaoming Zhu","doi":"10.1002/ajoc.70508","DOIUrl":"10.1002/ajoc.70508","url":null,"abstract":"<div><div>The conversion of CO₂ into cyclic carbonates under mild conditions remained challenging due to the thermodynamic stability of CO₂. Herein, a series of glutarimide‐based ionic liquids was developed for the cycloaddition of CO₂ to epoxides. Among them, [BZTMA][GLU] exhibited the highest activity, affording chloropropylene carbonate in 99.5% yield at 70°C within 7 h using only 2 mol% catalyst under 0.1 MPa CO₂. Systematic variation of the cation ([BZTMA]⁺, [HDBU]⁺, [CH]⁺), and anion ([GLU]^–, [Im]^–, [Pth]^–) revealed that catalytic performance was governed by a balance between CO₂ absorption capacity and cation‐anion interaction strength; excessively strong ion pairing counteracted the benefit of high CO₂ absorption. The catalyst was readily recovered and retained 95.9% yield after eight cycles. Substrate scope studies demonstrated that steric hindrance of both the epoxide and the anion critically influenced reactivity. This work established a clear structure‐activity relationship for the rational design of ionic liquid catalysts in CO₂ fixation.</div></div><div>The conversion of CO₂ into cyclic carbonates under mild conditions remained challenging due to the thermodynamic stability of CO₂. Herein, a series of glutarimide‐based ionic liquids was developed for the cycloaddition of CO₂ to epoxides. Among them, [BZTMA][GLU] exhibited the highest activity, affording chloropropylene carbonate in 99.5% yield at 70°C within 7 h using only 2 mol% catalyst under 0.1 MPa CO₂. Systematic variation of the cation ([BZTMA]⁺, [HDBU]⁺, [CH]⁺), and anion ([GLU]^–, [Im]^–, [Pth]^–) revealed that catalytic performance was governed by a balance between CO₂ absorption capacity and cation‐anion interaction strength; excessively strong ion pairing counteracted the benefit of high CO₂ absorption. The catalyst was readily recovered and retained 95.9% yield after eight cycles. Substrate scope studies demonstrated that steric hindrance of both the epoxide and the anion critically influenced reactivity. This work established a clear structure‐activity relationship for the rational design of ionic liquid catalysts in CO₂ fixation.</div><div>Synergistic catalytic mechanism of glutarimide ionic liquids in atmospheric pressure cycloaddition of CO₂ with epichlorohydrin.\u0000<span><figure><span><img><ol><li><span><span>Download: <span>Download high-res image (35KB)</span></span></span></li><li><span><span>Download: <span>Download full-size image</span></span></span></li></ol></span></figure></span></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 8","pages":"Article e70508"},"PeriodicalIF":2.3,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148752826","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":"N‐Phenacylpyridinium Salts‐Involved Formal Cyclization Reactions to Access Spiro[cyclopropane‐1,3'‐indolines]","authors":"Jinyan Liang,&nbsp;Yanjing Zheng,&nbsp;Kejing Shi,&nbsp;Donghui Guo,&nbsp;Shoujie Shen","doi":"10.1002/ajoc.70512","DOIUrl":"10.1002/ajoc.70512","url":null,"abstract":"<div><div>A novel formal (2 + 1) cyclization reaction between iminoindoline‐derived alkenes and N‑phenacylpyridinium salts has been developed to enable the efficient assembly of spiro[cyclopropane‐1,3'‐indolines] with excellent yields. A related one‐pot formal (1 + 1 + 1) cyclization reaction among iminoindolines, aldehydes, and N‑phenacylpyridinium salts has also been designed to construct the same spiroskeletons efficiently. The mild reaction conditions, the broad scope of substrates, and the promising scale‐up potential embody the synthetic superiority of these two processes.</div></div><div>A novel formal (2 + 1) cyclization reaction between iminoindoline‐derived alkenes and N‑phenacylpyridinium salts has been developed to enable the efficient assembly of spiro[cyclopropane‐1,3'‐indolines] with excellent yields. A related one‐pot formal (1 + 1 + 1) cyclization reaction among iminoindolines, aldehydes, and N‑phenacylpyridinium salts has also been designed to construct the same spiroskeletons efficiently. The mild reaction conditions, the broad scope of substrates, and the promising scale‐up potential embody the synthetic superiority of these two processes.</div><div>We report novel formal (2 + 1) and one‐pot formal (1 + 1 + 1) cyclization reactions mediated by N‑phenacylpyridinium salts for efficient assembly of spiro[cyclopropane‐1,3'‐indolines] with excellent yields and broad substrate scope under mild reaction conditions.\u0000<span><figure><span><img><ol><li><span><span>Download: <span>Download high-res image (41KB)</span></span></span></li><li><span><span>Download: <span>Download full-size image</span></span></span></li></ol></span></figure></span></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"15 8","pages":"Article e70512"},"PeriodicalIF":2.3,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148753033","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}