Chinese Journal of Chemistry最新文献

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Rhodium(III)-Catalyzed Directing Group-Enabled Unsymmetrical Three-Component Diamination of Alkenes 铑(III)催化定向基团使烯烃不对称三组分二化
IF 5.7 1区 化学
Chinese Journal of Chemistry Pub Date : 2026-08-01 Epub Date: 2026-07-14 DOI: 10.1002/cjoc.70682
Ziwei Lin, Yulong Kang, Fen Wang, Xingwei Li
{"title":"Rhodium(III)-Catalyzed Directing Group-Enabled Unsymmetrical Three-Component Diamination of Alkenes","authors":"Ziwei Lin,&nbsp;Yulong Kang,&nbsp;Fen Wang,&nbsp;Xingwei Li","doi":"10.1002/cjoc.70682","DOIUrl":"https://doi.org/10.1002/cjoc.70682","url":null,"abstract":"<div>\u0000 \u0000 <p>Substituted 1,2-diamines are common structural motifs in natural products and bioactive molecules, and their regioselective synthesis remains a pivotal challenge in organic chemistry. Herein, we report a Rh(III)-catalyzed directing group enabled unsymmetrical three- component diamination of alkenes (bearing thioether or amide directing groups), anilines, and dioxazolones for the efficient construction of 1,3-diamine derivatives. Under the optimized conditions, a broad range of anilines bearing electron-withdrawing substituents (<i>e.g</i>., –NO<sub>2</sub>, –CF<sub>3</sub>, –COOMe) are well tolerated, affording the desired products in moderate to excellent yields (61%–92%) with excellent regioselectivities (&gt;20 : 1). Notably, anilines with electron-donating groups exhibit low reactivity, furnishing the desired products in poor yields. In contrast, the aryl ring of the thioether substrate can accommodate both electron-withdrawing and electron-donating groups without compromising reaction efficiency and selectivity. Additionally, both thioether and amide directed alkenes are compatible with the catalytic system. Mechanistic studies, including radical trapping experiments, control reactions, and high-resolution mass spectrometry analysis, reveal that the reaction proceeds through a sulfur- or amide-directed rhodacycle intermediate rather than an aziridine pathway. The directing group plays a key role in controlling both reactivity and regioselectivity by facilitating the formation of a stable five- or six-membered metallacycle intermediates. The synthetic utility of this methodology is further demonstrated by gram-scale synthesis and versatile derivatizations of the products, enabling the rapid construction of unsymmetrical diamine compound libraries. In summary, we have developed a Rh(III)-catalyzed protocol for the regioselective synthesis of unsymmetrical 1,2-diamines. This method features high regioselectivity, operational simplicity, and broad substrate scope, providing a practical and robust entry to structurally diverse diamines for applications in complex molecule synthesis and medicinal chemistry.</p>\u0000 <p></p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"44 17","pages":"2911-2917"},"PeriodicalIF":5.7,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148652496","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Tailoring Crystalline Self-Assembled Monolayers via Skeletal Isomerization for Exceptional Efficiency and Reproducibility in Organic Solar Cells 在有机太阳能电池中,通过骨架异构化剪裁晶体自组装单层,以获得卓越的效率和可重复性
IF 5.7 1区 化学
Chinese Journal of Chemistry Pub Date : 2026-08-01 Epub Date: 2026-07-07 DOI: 10.1002/cjoc.70657
Yaqi Pei, Jiawei Deng, Hansheng Chen, Jiaping Xie, Xiaozhong Shuai, Jie Zhou, Hyeong Hui Kim, Han Young Woo, Feiyan Wu, Jiabin Liu, Chen Xie, Lie Chen
{"title":"Tailoring Crystalline Self-Assembled Monolayers via Skeletal Isomerization for Exceptional Efficiency and Reproducibility in Organic Solar Cells","authors":"Yaqi Pei,&nbsp;Jiawei Deng,&nbsp;Hansheng Chen,&nbsp;Jiaping Xie,&nbsp;Xiaozhong Shuai,&nbsp;Jie Zhou,&nbsp;Hyeong Hui Kim,&nbsp;Han Young Woo,&nbsp;Feiyan Wu,&nbsp;Jiabin Liu,&nbsp;Chen Xie,&nbsp;Lie Chen","doi":"10.1002/cjoc.70657","DOIUrl":"https://doi.org/10.1002/cjoc.70657","url":null,"abstract":"<div>\u0000 \u0000 <p>The carbazolyl phosphonic acid-based self-assembled molecules (SAMs) are a promising candidate as hole transport layers (HTLs) for organic solar cells (OSCs). However, the SAM films tend to have incomplete surface coverage on the electrode, such that interfacial defects adversely affecting device performance and reproducibility. To address this issue, we design three asymmetric SAMs (4PACz-1N, 4PACz-2N, and 4PACz-3N) featuring isomerized naphthyl-carbazole skeletons. Skeleton isomerization simultaneously regulates dipole properties to elevate the work function of ITO anodes and minimizes energy barriers for hole extraction. Meanwhile, the conjugation skeleton expansion can further promote molecular stacking and reduce surface energy, leading to more complete coverage on the ITO and more intimate contact with the active layer, thereby enhancing the reproducibility of the device. Consequently, these isomerized SAMs demonstrate synergistic improvements in charge extraction efficiency, device reproducibility, and interfacial stability. These features significantly improve charge dynamics and interfacial stability, and demonstrate universal applicability in numerous systems. Notably, binary devices based on 4PACz-1N can achieve an excellent efficiency of 20.27% with outstanding device stability. This work highlights the significance of the skeleton isomerization strategy for developing highly efficient HTL.</p>\u0000 <p></p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"44 17","pages":"2870-2880"},"PeriodicalIF":5.7,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148652513","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Enantioselective Synthesis of 3-Hydroxy Oxindoles via NHC-Catalyzed [2 + 2] Cycloaddition nhc催化[2 + 2]环加成对映选择性合成3-羟基氧吲哚
IF 5.7 1区 化学
Chinese Journal of Chemistry Pub Date : 2026-08-01 Epub Date: 2026-07-07 DOI: 10.1002/cjoc.70672
Bin Liu, Guanbing Wei, Liang Guo, Xuebin Chen, Tian-Yuan Zhang, Xiangkai Kong, Qing He, Rong-Hua Wang, Jianta Wang, Jun Sun, Lei Tang
{"title":"Enantioselective Synthesis of 3-Hydroxy Oxindoles via NHC-Catalyzed [2 + 2] Cycloaddition","authors":"Bin Liu,&nbsp;Guanbing Wei,&nbsp;Liang Guo,&nbsp;Xuebin Chen,&nbsp;Tian-Yuan Zhang,&nbsp;Xiangkai Kong,&nbsp;Qing He,&nbsp;Rong-Hua Wang,&nbsp;Jianta Wang,&nbsp;Jun Sun,&nbsp;Lei Tang","doi":"10.1002/cjoc.70672","DOIUrl":"https://doi.org/10.1002/cjoc.70672","url":null,"abstract":"<div>\u0000 \u0000 <p>Chiral 3-hydroxy-3-substituted oxindoles represent privileged heterocyclic cores ubiquitous in pharmaceuticals, lead compounds, and bioactive natural products. Despite the establishment of numerous synthetic methodologies for the asymmetric construction of 3-hydroxy-3-substituted oxindoles, the enantioselective construction of such frameworks bearing multiple stereogenic centers under mild conditions remains challenging. Most existing approaches require transition-metal catalysts, harsh reaction conditions, or prefunctionalized starting materials, which limit their practical utility. In recent years, <i>N</i>-heterocyclic carbenes (NHCs) have emerged as powerful and efficient organic catalysts in an expanding range of asymmetric transformations. Many novel activation modes, including the generation of acyl azoliums and enolates, have been developed using NHCs as key organocatalysts. Consequently, diverse functional and biologically active molecules have been constructed via NHC-catalyzed reactions. Among these intermediates, enolate intermediates play a pivotal role in NHC catalysis and are widely utilized as two-carbon (2C) synthons in [2 + 4] cycloadditions to construct heterocyclic compounds. However, exploiting alternative [2 + <i>n</i>] annulation modes, particularly [2 + 2] cycloadditions, remains of considerable scientific interest and practical relevance due to the potential for generating strained β-lactone intermediates that can be further elaborated. Herein, we report an NHC-catalyzed enantio- and diastereoselective [2 + 2] cycloaddition/ring-opening sequence that provides quick and efficient access to structurally diverse 3-substituted-3-hydroxyoxindoles bearing two chiral centers. The reaction tolerates a broad scope of substrates, affording the products in generally moderate to excellent yields with good optical purities. Moreover, the reaction is scalable to a 10-fold loading, delivering the target product in 84% isolated yield with 96 : 4 er and &gt;20 : 1 dr. Notably, the obtained products can undergo diverse further derivatizations without erosion of stereoselectivity, underscoring their utility as chiral building blocks. We proposed a plausible reaction mechanism involving the formation of an NHC-bound enolate followed by a stereoselective [2 + 2] cycloaddition to generate a spirocyclic β-lactone intermediate, which then undergoes ring opening. Key intermediates were detected by HRMS and NMR, providing solid evidence for the proposed pathway.</p>\u0000 <p></p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"44 17","pages":"2881-2886"},"PeriodicalIF":5.7,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148652514","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Inside Cover Picture 内页图片
IF 5.7 1区 化学
Chinese Journal of Chemistry Pub Date : 2026-08-01 DOI: 10.1002/cjoc.70727
{"title":"Inside Cover Picture","authors":"","doi":"10.1002/cjoc.70727","DOIUrl":"https://doi.org/10.1002/cjoc.70727","url":null,"abstract":"<p>The electrocatalytic reductive transformation of thioamides has been challenging due to catalyst poisoning by sulfur-containing species. An electrohydrogenative coupling of thioamides with olefins is achieved using a cobalt catalyst, with protons as the hydrogen source. This protocol enables highly selective synthesis of α-branched amines, including deuterium-labeled analogues, with excellent functional group tolerance and late-stage modification. More details are discussed in the article by Liu <i>et al</i>. on pages 2847—2854.\u0000\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"44 17","pages":""},"PeriodicalIF":5.7,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cjoc.70727","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148652433","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Visible-Light-Induced Site-Selective C(sp2/sp3)-H Functionalization toward Epoxides 可见光诱导的位点选择性C(sp2/sp3)-H对环氧化物的功能化
IF 5.7 1区 化学
Chinese Journal of Chemistry Pub Date : 2026-08-01 Epub Date: 2026-07-15 DOI: 10.1002/cjoc.70646
Mengjia Wang, Zhiming Zhu, Shuaiqi Lu, Xiaoyu Liu, Ziyang Li, Jiang Duan, Chao Shu
{"title":"Visible-Light-Induced Site-Selective C(sp2/sp3)-H Functionalization toward Epoxides","authors":"Mengjia Wang,&nbsp;Zhiming Zhu,&nbsp;Shuaiqi Lu,&nbsp;Xiaoyu Liu,&nbsp;Ziyang Li,&nbsp;Jiang Duan,&nbsp;Chao Shu","doi":"10.1002/cjoc.70646","DOIUrl":"https://doi.org/10.1002/cjoc.70646","url":null,"abstract":"<div>\u0000 \u0000 <p>This work presents the first practical and modular strategy for visible-light-induced, site-selective C(sp<sup>2</sup>/sp<sup>3</sup>)-H functionalization of inert C–H bonds in feedstock chemicals. Utilizing tetrabutylammonium decatungstate (TBADT) as a hydrogen atom transfer photocatalyst, a broad range of substrates, including ethers, thioethers, amides, alkanes, aldehydes, and complex bio-related molecules, undergo efficient epoxidation with allylic peroxides under mild, oxidant-free, and operationally simple conditions. The protocol affords diverse, highly functionalized oxiranes with excellent site-selectivity and wide functional group tolerance at room temperature under 390 nm light irradiation. Its synthetic utility is further demonstrated by gram-scale synthesis and versatile post-transformations, such as ring-opening, reduction, halogenation, azidation, and one-pot cyclizations. Molecular docking studies reveal that the resulting epoxides exhibit favorable binding interactions with kinase proteins, highlighting potential applications in biochemical research and drug development. This visible-light-mediated C–H epoxidation offers a green, efficient, and modular route to high-value oxiranes, expanding the toolkit for organic synthesis and medicinal chemistry.</p>\u0000 <p></p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"44 17","pages":"2861-2869"},"PeriodicalIF":5.7,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148652495","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Enantioselective Synthesis of α-Hydroxy-β-Amino Ketones via Engineered ThDP-Dependent Enzyme Catalysis 通过工程thdp依赖酶催化对映选择性合成α-羟基-β-氨基酮
IF 5.7 1区 化学
Chinese Journal of Chemistry Pub Date : 2026-08-01 Epub Date: 2026-06-30 DOI: 10.1002/cjoc.70659
Linli Dai, Dongqi Wu, Keke Zou, Huangong Li, Jiale Sun, Jingyu Zhang, Xueting Liu, Guoliang Zhu, Lixin Zhang, Yongtao Xie
{"title":"Enantioselective Synthesis of α-Hydroxy-β-Amino Ketones via Engineered ThDP-Dependent Enzyme Catalysis","authors":"Linli Dai,&nbsp;Dongqi Wu,&nbsp;Keke Zou,&nbsp;Huangong Li,&nbsp;Jiale Sun,&nbsp;Jingyu Zhang,&nbsp;Xueting Liu,&nbsp;Guoliang Zhu,&nbsp;Lixin Zhang,&nbsp;Yongtao Xie","doi":"10.1002/cjoc.70659","DOIUrl":"https://doi.org/10.1002/cjoc.70659","url":null,"abstract":"<div>\u0000 \u0000 <p><i>α</i>-Hydroxy-<i>β</i>-amino ketones are key structural motifs in many bioactive compounds, yet their asymmetric synthesis remains challenging. Although numerous approaches for accessing simple amino alcohols are well established, methods specifically targeting the construction of the <i>α</i>-hydroxy-<i>β</i>-amino ketones motif have been rarely explored. Herein, we report a green biocatalytic approach to access these scaffolds via cross-benzoin condensation of <i>α</i>-amino aldehydes and aryl aldehydes using an engineered ThDP-dependent enzyme. Through protein engineering of benzaldehyde lyase from <i>Pseudomonas fluorescens</i> (<i>Pf</i>BAL), the variant A28G was identified that efficiently catalyzes this transformation. Compared with the wild-type enzyme, which gave only 33% yield of the desired product along with 49% self-benzoin byproduct, the A28G mutant significantly improved the cross-coupling efficiency while reducing the homocoupling side reaction to just 3%. Under optimized aqueous conditions, the <i>Pf</i>BAL A28G catalyst accommodated a broad range of aryl aldehydes bearing electron-withdrawing or electron-donating substituents, as well as heteroaromatic (furan, thiophene) and disubstituted derivatives, delivering the corresponding <i>α</i>-hydroxy-<i>β</i>-amino ketones in up to 98% isolated yields with excellent enantioselectivities (up to &gt;99% ee). The practical utility of this method was demonstrated by gram-scale synthesis (1.13 g of product <b>3a</b>) with 81% yield and retaining 96% ee. Molecular dynamics simulations revealed that the A28G mutation shortens the attack distance between the Breslow intermediate and the <i>α</i>-amino aldehyde acceptor from 6.4 Å to 4.5 Å, accounting for the enhanced reactivity. Moreover, differential binding of the product enantiomers to the active site explains the strict <i>R</i>-configuration control. This work not only provides a green, atom-economic, and highly stereoselective route to enantioenriched <i>α</i>-hydroxy-<i>β</i>-amino ketones under mild aqueous conditions but also expands the synthetic repertoire of ThDP-dependent enzymes to nitrogen-functionalized aldehyde acceptors, opening new avenues for biocatalytic C–C bond formation in pharmaceutical chemistry and natural product synthesis.</p>\u0000 <p></p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"44 17","pages":"2855-2860"},"PeriodicalIF":5.7,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148652490","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Metal-Free [5 + 2] Cyclization of Photogenerated Siloxyketenes and Vinyl Aziridines for the Synthesis of Azepanones 光合成硅氧酮和乙烯基叠氮醚的无金属[5 + 2]环化合成氮酮
IF 5.7 1区 化学
Chinese Journal of Chemistry Pub Date : 2026-08-01 Epub Date: 2026-07-07 DOI: 10.1002/cjoc.70680
Lingyun Yao, Xiuhui Li, Xiang Luo, Quannan Wang, Xusheng Shao, Wei-Ping Deng
{"title":"Metal-Free [5 + 2] Cyclization of Photogenerated Siloxyketenes and Vinyl Aziridines for the Synthesis of Azepanones","authors":"Lingyun Yao,&nbsp;Xiuhui Li,&nbsp;Xiang Luo,&nbsp;Quannan Wang,&nbsp;Xusheng Shao,&nbsp;Wei-Ping Deng","doi":"10.1002/cjoc.70680","DOIUrl":"https://doi.org/10.1002/cjoc.70680","url":null,"abstract":"<div>\u0000 \u0000 <p>Ketenes constitute a versatile and highly reactive class of intermediates with widespread utility in modern organic synthesis. Among them, siloxyketenes, a class of oxygen-substituted variants, generated <i>in situ</i> from α-ketoacylsilanes through a photoinduced [1,3]-silyl migration, have garnered considerable attention due to their distinctive structural features. However, their synthetic utility has been confined to the construction of four- to six-membered rings. The development of methods that exploit these intermediates for the assembly of medium-sized rings remains exceedingly limited and is therefore highly desirable. Herein, we developed a metal-free, visible-light-driven [5 + 2] cyclization reaction for the synthesis of azepanone derivatives. Under irradiation of blue LEDs at 20 °C, α-ketoacylsilanes and vinyl aziridine were used as readily available substrates to realize this cyclization. The reaction features mild reaction conditions, operational simplicity, a broad substrate scope, and it generates diverse azepanones bearing a tertiary alcohol motif in good to excellent yields (up to 96%). The reaction proceeds via a photochemically induced [1,3]-silyl migration to form reactive siloxyketenes, followed by nucleophilic addition and a ring-closing process. This work expands the application of α-ketoacylsilanes as siloxyketene precursors and provides a concise and efficient approach to constructing medium-sized rings under mild conditions.</p>\u0000 <p></p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"44 17","pages":"2905-2910"},"PeriodicalIF":5.7,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148652511","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Rh-Catalyzed Asymmetric Hydrogenation of 4-Quinolone-2-carboxylic Acids: Direct Access to Versatile Chiral 2,3-Dihydroquinolones 铑催化4-喹诺酮-2-羧酸的不对称加氢:直接获得多用途手性2,3-二氢喹诺酮
IF 5.7 1区 化学
Chinese Journal of Chemistry Pub Date : 2026-08-01 Epub Date: 2026-06-30 DOI: 10.1002/cjoc.70685
Shaonan An, Zhuang Nie, Di Liu, Meiling Ma, Xiaoshuai Niu, Yuheng Guo, Shaohua Wang, Shengyong Zhang, Lin Yao
{"title":"Rh-Catalyzed Asymmetric Hydrogenation of 4-Quinolone-2-carboxylic Acids: Direct Access to Versatile Chiral 2,3-Dihydroquinolones","authors":"Shaonan An,&nbsp;Zhuang Nie,&nbsp;Di Liu,&nbsp;Meiling Ma,&nbsp;Xiaoshuai Niu,&nbsp;Yuheng Guo,&nbsp;Shaohua Wang,&nbsp;Shengyong Zhang,&nbsp;Lin Yao","doi":"10.1002/cjoc.70685","DOIUrl":"https://doi.org/10.1002/cjoc.70685","url":null,"abstract":"<div>\u0000 \u0000 <p>This work reports the first example of rhodium-catalyzed asymmetric hydrogenation of 4-quinolone-2-carboxylic acids, providing direct access to chiral 2,3-dihydro-4-quinolones—a privileged scaffold in medicinal chemistry. Through systematic optimization of ligands, metal precursors, and solvents, the optimal catalytic system was identified as Rh(COD)<sub>2</sub>OTf combined with the chiral bisphosphine ligand (<i>R</i>,<i>R</i>)-Ph-BPE. The reaction proceeds smoothly under 40 atm of H<sub>2</sub> in <i>t</i>-BuOH at 80 °C, affording a broad range of enantioenriched 2,3-dihydro-4-quinolones in moderate to excellent yields (40%–99%) and with high enantioselectivities (up to 99% <i>ee</i>). A broad range of substituents, including <i>N</i>-alkyl, <i>N</i>-benzyl, and electron-donating or electron-withdrawing groups on the quinolone core, are well tolerated, though the position and electronic nature of the substituents can affect enantioselectivity. Deuterium labeling experiments using D<sub>2</sub>/<i>t</i>-BuOH and D<sub>2</sub>/<i>t</i>-BuOD confirmed that molecular hydrogen (H<sub>2</sub>/D<sub>2</sub>) is the exclusive hydrogen source, with no direct participation of the protic solvent in the reduction step. Control experiments using C2-methyl or C2-ester substituted quinolones resulted in no conversion, demonstrating that the free carboxylic acid group is essential for substrate coordination to the rhodium center. Based on these findings and previous mechanistic studies, a plausible catalytic cycle is proposed involving oxidative addition of H<sub>2</sub>, carboxylate-directed substrate coordination, migratory insertion into the C=C bond, and reductive elimination. Gram-scale reactions successfully delivered the desired products in high yields (92%–95%) and enantioselectivity (88% <i>ee</i>). Furthermore, product derivatization successfully furnished a new class of non-natural chiral amino esters, underscoring the synthetic utility of this method for constructing pharmaceutically relevant scaffolds.</p>\u0000 <p></p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"44 17","pages":"2927-2932"},"PeriodicalIF":5.7,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148652489","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Modular Enantioselective Synthesis of Tetrahydropyridazines by Palladium-Catalyzed Aminoalkenylation/Aminoarylation Reaction 钯催化氨基烯基化/氨基芳基化反应的模块化对映选择性合成四氢吡啶类化合物
IF 5.7 1区 化学
Chinese Journal of Chemistry Pub Date : 2026-07-15 Epub Date: 2026-06-11 DOI: 10.1002/cjoc.70650
Cangzhu Hu, Xuefeng Deng, Shuaijie Wu, Shuwei Zhang, Chenghao Zhu, Qiang Dai, Junliang Zhang, Lei Wang
{"title":"Modular Enantioselective Synthesis of Tetrahydropyridazines by Palladium-Catalyzed Aminoalkenylation/Aminoarylation Reaction","authors":"Cangzhu Hu,&nbsp;Xuefeng Deng,&nbsp;Shuaijie Wu,&nbsp;Shuwei Zhang,&nbsp;Chenghao Zhu,&nbsp;Qiang Dai,&nbsp;Junliang Zhang,&nbsp;Lei Wang","doi":"10.1002/cjoc.70650","DOIUrl":"https://doi.org/10.1002/cjoc.70650","url":null,"abstract":"<div>\u0000 \u0000 <p>Chiral 1,4,5,6-tetrahydropyridazine core has emerged as valuable structural motifs in drug discovery, and has been recognized that the identified stereocenter of this structure has a significant impact on activity. Nevertheless, the catalytic asymmetric synthesis of such frameworks with clearly defined stereocenters remains a significant challenge, primarily due to the inherent difficulty in achieving stereo control during the cyclization process, as well as the limited availability of broadly applicable efficient catalytic system. In this work, a novel palladium-catalyzed enantioselective aminoalkenylation and aminoarylation of <i>γ,δ</i>-unsaturated hydrazones with aryl or alkenyl halides is described. The use of a sterically demanding Xu-Phos ligand ensures excellent chemoselectivity and enantioselectivity. This protocol provides an efficient and practical strategy for the synthesis of structurally diverse chiral tetrahydropyridazines bearing alkenyl and aryl functionalities in good yields and high enantioselectivities under mild reaction conditions. Notably, preliminary mechanistic investigations indicate that the <i>syn</i>-azapalladation was found to be the dominant pathway and might elucidate the high enantioselectivity in the cyclization process.</p>\u0000 <p></p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"44 16","pages":"2772-2778"},"PeriodicalIF":5.7,"publicationDate":"2026-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148532999","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Inside Cover Picture 内页图片
IF 5.7 1区 化学
Chinese Journal of Chemistry Pub Date : 2026-07-15 DOI: 10.1002/cjoc.70712
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