Chinese Journal of Chemistry最新文献

{"title":"Multiscale Diagnosis of Lithium-Ion Battery Degradation under Extreme Operating Conditions with Integrated Data-Driven and Post-Mortem Validation","authors":"Shuhan Mo,&nbsp;Yuefeng Su,&nbsp;Jinyang Dong,&nbsp;Yimin Wei,&nbsp;Tinglu Song,&nbsp;Yun Lu,&nbsp;Kang Yan,&nbsp;Rui Tang,&nbsp;Guangjin Zhao,&nbsp;Jinding Liang,&nbsp;Xixiu Shi,&nbsp;Bowen Li,&nbsp;Ning Li,&nbsp;Lai Chen,&nbsp;Feng Wu","doi":"10.1002/cjoc.70500","DOIUrl":"https://doi.org/10.1002/cjoc.70500","url":null,"abstract":"<div>\u0000 \u0000 <p>Lithium-ion batteries subjected to extreme operating conditions—such as high temperature, high C-rates, and deep overdischarge— exhibit rapid and coupled aging behaviors that are challenging to disentangle using conventional diagnostics. While purely data-driven models often lack interpretability (\"black-box\"), physics-based methods typically require measurements unavailable in practical applications. To bridge this gap, we propose the SIX-ICA framework, an interpretable machine learning approach that integrates Incremental Capacity Analysis (ICA) features with an XGBoost regressor and SHAP analysis. By extracting mechanism-informed ICA peak features from routine cycling data, the framework achieves robust State-of-Health (SOH) estimation. Crucially, SHAP analysis provides transparent feature attribution, linking statistical inputs directly to degradation pathways. Validated on LiFePO₄/graphite pouch cells cycled at 65 °C and 3 C (comparing 2.5 V vs. 1.0 V cutoffs), the framework identifies Loss of Lithium Inventory (LLI) as the primary driver of capacity fade, noting its significant intensification under deep over-discharge, while Loss of Active Material (LAM) plays a secondary role. These findings are corroborated by OCV fitting and post-mortem characterization. This workflow advances interpretable SOH diagnostics under extreme conditions and offers a scalable route for other battery chemistries.</p>\u0000 <p></p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"44 10","pages":"1608-1616"},"PeriodicalIF":5.5,"publicationDate":"2026-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147696314","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}

{"title":"Electrochemical-Mechanical Coupled Model for Macro-Scale Stress Prediction of Nickel-Rich NCM Cathodes in Li-ion Batteries†","authors":"Qinghe Hu,&nbsp;Xingmin He,&nbsp;Shuai Zheng,&nbsp;Wei Li,&nbsp;Zehui Zhao,&nbsp;Peng Tan","doi":"10.1002/cjoc.70492","DOIUrl":"https://doi.org/10.1002/cjoc.70492","url":null,"abstract":"<div>\u0000 \u0000 <p>Ni-rich LiNi_<i>x</i>Co_<i>y</i>Mn_<i>z</i>O₂ (NCM) materials are regarded as one of the most promising candidates for next-generation lithium-ion batteries due to their high specific capacity. However, their mechanical degradation during cycling leads to significant capacity fading. Electrochemical–mechanical coupled modeling is an effective strategy for understanding the underlying mechanisms of mechanical degradation. Nevertheless, studies involving the simulation and experimental validation of macroscopic electrode stress remain insufficient. This work delineates the multi-scale lithiation-induced strain process in NCM materials and establishes a three-dimensional heterogeneous electrochemical-mechanical coupled model that successfully predicts the macroscopic stress evolution in NCM811 electrodes. Sufficient physical justification and experimental validation are provided for the isotropic simplification of anisotropic single-crystal particles. The simulations reveal the rate performance of particles across different sizes, identifying potential locations of mechanical failure. These findings underscore the importance of macroscopic stress signals in reflecting the electrochemical state of electrodes and provide a validated tool for analyzing battery behavior based on stress information.</p>\u0000 <p></p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"44 10","pages":"1506-1514"},"PeriodicalIF":5.5,"publicationDate":"2026-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147696335","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}

{"title":"Pd-Catalyzed Dihalogenative Endo Cyclization of 1,6-Enynes","authors":"Zhengyu Han,&nbsp;Xiang Li,&nbsp;Jing Huang,&nbsp;Shan Zhong,&nbsp;Shuxuan Liu,&nbsp;Weimin Li,&nbsp;Jianwei Sun,&nbsp;Hai Huang","doi":"10.1002/cjoc.70516","DOIUrl":"https://doi.org/10.1002/cjoc.70516","url":null,"abstract":"<div>\u0000 \u0000 <p>Described here is an unusual palladium-catalyzed dihalogenative <i>endo</i> cyclization of unactivated 1,6-enynes. In sharp contrast to previous related studies, which have long been restricted to activated electron-deficient enynes and/or exclusively resulted in <i>exo</i> cyclization, the present process for the first time enables unactivated 1,6-enynes to overcome the inherent kinetic tendency toward <i>5-exo-trig</i> cyclization and lead to the kinetically disfavored <i>6-endo-trig</i> pathway. This distinctive cyclization mode is inconsistent with classical Baldwin's rules, which typically favor the formation of five-membered rings through <i>exo-trig</i> cyclization due to kinetic advantages and lower energy barriers. Both dibromination and dichlorination transformations are successfully achieved under optimized reaction conditions, employing a palladium catalyst in combination with a copper halide salt, an appropriate base and solvent system to ensure high reactivity, excellent regioselectivity, and outstanding stereoselectivity. This synthetic strategy facilitates the rapid and efficient construction of highly functionalized six-membered heterocycles, including piperidines and tetrahydropyrans, as well as carbocycles, all of which exhibit satisfactory overall performance across a broad substrate scope encompassing aryl, heteroaryl, and alkyl substituents on the enyne scaffold. The resulting products possess two versatile carbon-halogen bonds, including C(sp²)-X and C(sp³)-X type, and a stereodefined olefin with excellent &gt;20 : 1 <i>E</i>/<i>Z</i> selectivity, rendering them valuable building blocks for subsequent organic transformations. Control experiments further confirm the essential roles of both palladium and copper salts in promoting the reaction, while preliminary DFT calculations shed light on the origin of reaction selectivity and the cyclization mechanism. Collectively, all these features underscore the significant synthetic utility of this newly developed cyclization protocol in modern organic synthesis.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"44 10","pages":"1631-1637"},"PeriodicalIF":5.5,"publicationDate":"2026-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147696357","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}

{"title":"Bimetallic Hybridization Induced Multi-polarization Loss in Multiphase Solid Solution for Electromagnetic Wave Absorption†","authors":"Mengjun Han,&nbsp;Zirui Jia,&nbsp;Di Lan,&nbsp;Zhenguo Gao,&nbsp;Guanglei Wu","doi":"10.1002/cjoc.70494","DOIUrl":"10.1002/cjoc.70494","url":null,"abstract":"<div>\u0000 \u0000 <p>Aiming at the polarization loss bottleneck in electromagnetic wave (EMW) absorbing materials, we propose a new bimetallic hybrid strategy towards multiphase solid solutions to increase multiple polarization losses. Assisted by polydopamine (PDA) as crystalline phase inducer, Mo/W substances were anchored <i>in situ</i> on carbon networks. As a result, a carbon-supported MoC_1–<i>x</i>/WC/W₂C/WC_1–<i>x</i> heterostructure was formed. This process leads to Mo migration and W occupying vacancies, resulting in vacancy/substitution defects. Simultaneously, Li⁺ is inserted into the solid solution to form an interstitial structure. Due to the synergistic effect of multiple polarization losses, the Mo2W-900 solid solution achieved excellent EMW absorption performance. The minimum reflection loss (RL_min) at a thickness of 2.5 mm is –65.92 dB, and it has a maximum effective absorption bandwidth (EAB_max) of 6.16 GHz at only 2.1 mm. This paper establishes a new type of multi-loss polarization model for solid-solution absorbers, providing important theoretical guidance for the design of the next generation of hybrid absorbers.</p>\u0000 <p></p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"44 10","pages":"1525-1538"},"PeriodicalIF":5.5,"publicationDate":"2026-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147381524","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}

{"title":"Iron-Mediated Electrochemical Cyclopropanation of Borodiiodomethane with Alkenes†","authors":"Jie Li,&nbsp;Yingying Pan,&nbsp;Xin Wang,&nbsp;Xuefeng Tan","doi":"10.1002/cjoc.70509","DOIUrl":"https://doi.org/10.1002/cjoc.70509","url":null,"abstract":"<p>Cyclopropane is a unique ring motif widely incorporated into pharmaceuticals to enhance their potency. Developing synthetic methods for the efficient construction of cyclopropanes, particularly those with functional groups, is of both practical significance and academic interest. Among the reported methods, the reduction of <i>gem</i>-dihalides followed by cyclization with alkenes represents one of the most efficient and straightforward [2+1] approaches. However, most references rely on photochemical pathways, which severely limit practical applications. Additionally, electrochemical catalytic reduction of halides has gained significant attention in recent years, primarily using nickel and cobalt catalysts. In this study, we introduce an iron-mediated electrochemical reduction of borodiiodomethane, followed by cyclopropanation with alkenes, enabling rapid fabrication of cyclopropylboronates. Substrates with a wide range of functional groups are well tolerated, demonstrating the ease of late-stage modifications. Gram-scale synthesis, conducted without extending reaction time and maintaining the same current density, yielded similar results, highlighting the method's practical application. The boronate group on the cyclopropane can be easily transformed, paving the way for further applications in medicinal chemistry. Notably, mechanistic investigations, including control experiments and cyclic voltammetry studies, revealed that iron species—both the Fe salt and the Fe/2,2'-biquinoline complex—can effectively promote electrochemical cyclopropanation. Given that iron is an inexpensive material, its dual role as both sacrificial anode and promoter enhances the practicality of this method.</p><p></p>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"44 10","pages":"1565-1572"},"PeriodicalIF":5.5,"publicationDate":"2026-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cjoc.70509","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147696367","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}

{"title":"Photocatalytic Synthesis of α-Trifluoromethyl Amidines and α-Trifluoromethyl Imidates from Isocyanides and Trifluoroacetylsilanes†","authors":"Yuan Yao,&nbsp;Gang Zhou,&nbsp;Shanshan Liu,&nbsp;Xiaotian Qi,&nbsp;Xiaoqian He,&nbsp;Xiao Shen","doi":"10.1002/cjoc.70515","DOIUrl":"https://doi.org/10.1002/cjoc.70515","url":null,"abstract":"<div>\u0000 \u0000 <p><i>α-</i>Trifluoromethyl amidines and imidates represent privileged molecular scaffolds due to the prevalence of amidine/imidate motifs in bioactive compounds and functional materials, coupled with the ability of the CF₃ group to enhance key physicochemical and pharmacological properties. Nevertheless, general methods for their synthesis remain underdeveloped. Herein, we report a mild, metal- free photocatalytic strategy that enables the modular assembly of these valuable structures with perfect atom economy. The protocol involves the <i>in situ</i> generation of 3-(trifluoromethyl)ketenimines from readily accessible trifluoroacylsilanes and isocyanides, followed by nucleophilic trapping with anilines and phenols. This operationally simple method exhibits a broad substrate scope, high efficiency, and generally delivers products in good yields. Mechanistic investigations, supported by density functional theory (DFT) calculations, indicate that the reaction proceeds preferentially via a triplet carbene intermediate, and a plausible mechanism for the pivotal coupling step is proposed.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"44 10","pages":"1624-1630"},"PeriodicalIF":5.5,"publicationDate":"2026-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147696317","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}

{"title":"Construction of Carbazoles from 2-Bromobiaryls Using N2 as a N Source","authors":"Kai Wang,&nbsp;Chang-Cheng Wang,&nbsp;Yang Liao,&nbsp;Feng Liu,&nbsp;Dan-Dan Zhai,&nbsp;Zhang-Jie Shi","doi":"10.1002/cjoc.70502","DOIUrl":"https://doi.org/10.1002/cjoc.70502","url":null,"abstract":"<div>\u0000 \u0000 <p>Due to the high activation barriers associated with cleaving both C–H bonds and the N≡N triple bond, achieving C–N bond formation from relatively inert C–H bonds as carbon sources under mild conditions has long posed a major challenge in synthetic chemistry. To address this long-standing issue, we have developed a novel and straightforward approach for the synthesis of carbazoles, using N₂ as the nitrogen source and 2-bromobiaryls as the carbon partner through an engineered one-pot/two-step protocol. The key to this protocol lies in the <i>in-situ</i> generation of lithium nitride (Li₃N) from N₂ using lithium as the reductant, which serves as a primary intermediate. This intermediate then undergoes a Pd-catalyzed process involving successive C(sp²)–Br bond activation and intramolecular C(sp²)–H bond functionalization to form the target carbazole framework. Notably, this strategy exhibits a broad substrate scope, excellent tolerance towards various functional groups, and high regioselectivity. Leveraging this method, we have successfully synthesized a diverse range of high-value carbazoles directly from N₂, including biologically active natural alkaloids (such as the anti-HIV drug Glycoborine and the antiviral compound Clausine V), optoelectronic materials (<i>e.g</i>., 11,12-dihydroindolo[2,3-<i>a</i>]carbazole), and ¹⁵N-labeled carbazoles. This approach not only expands the scope of carbon sources suitable for nitrogen incorporation from N₂ but also paves potential pathways for the development of diverse catalytic systems, offering new opportunities for the efficient synthesis of nitrogen-containing heterocycles.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"44 10","pages":"1573-1578"},"PeriodicalIF":5.5,"publicationDate":"2026-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147696341","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}

{"title":"Catalytic Enantioselective Construction of Silicon-Stereogenic Silacarbocycles†","authors":"Xiuping Yuan,&nbsp;Kehan Jiao,&nbsp;Jiaqiong Sun,&nbsp;Qian Zhang,&nbsp;Tao Xiong","doi":"10.1002/cjoc.70499","DOIUrl":"https://doi.org/10.1002/cjoc.70499","url":null,"abstract":"&lt;div&gt;\u0000 \u0000 &lt;section&gt;\u0000 \u0000 &lt;h3&gt; Comprehensive Summary&lt;/h3&gt;\u0000 \u0000 &lt;p&gt;Silicon-stereogenic silacarbocycles constitute a privileged class of organosilicon compounds with wide-ranging applications in asymmetric synthesis, functional materials, and medicinal chemistry. This review provides a systematic overview of recent advances in catalytic enantioselective synthetic methods, organized by catalytic systems, and traces the evolution of key strategies—with particular emphasis on desymmetrization of prochiral precursors, alongside kinetic resolution (KR) and dynamic kinetic asymmetric transformation (DYKAT). The field was initially established through pioneering Pd-catalyzed transformations, notably the asymmetric ring-expansion of strained silacyclobutanes with alkynes—a fundamental methodology for constructing cyclic tetraorganosilicon stereocenters. Subsequently, Rh-catalyzed systems have emerged as highly versatile platforms, enabling diverse transformations including dehydrogenative C–H silylation for accessing monohydrosilanes and heterocycles, intramolecular hydrosilylation toward cyclic monohydrosilanes and spirosilabiindanes, and formal [2+2+2] cycloadditions for synthesizing dibenzosiloles and silaspiranes. Driven by economic and sustainability considerations, research has fruitfully expanded to encompass earth-abundant base metal catalysis. Ni-catalyzed systems facilitate efficient intramolecular aryl transfer and ring-expansion reactions, while Co- and Cu-catalyzed approaches enable sequential hydrosilylation cascades that construct silacycles bearing consecutive Si and C stereocenters. Concurrently, metal-free organocatalysis has emerged as a powerful sustainable alternative, with chiral &lt;i&gt;N&lt;/i&gt;-heterocyclic carbenes (NHCs), chiral phosphoric acids (CPAs), enamine catalysts, and confined imidodiphosphorimidates (IDPi) demonstrating remarkable efficacy in enantioselective desymmetrization processes. Despite substantial progress, we also offer a critical perspective on current methodologies, outline existing challenges and limitations, and highlight promising directions for future research. Current limitations include reliance on elaborate prochiral substrates and historical dependence on precious metals. Future efforts should focus on developing more efficient and atom-economical substrate synthesis, expanding sustainable catalytic systems including base-metal, organo-, and biocatalysis, integrating emerging technologies such as photocatalysis and electrocatalysis, and deepening mechanistic understanding to enable the rational design of advanced strategies such as DYKAT.&lt;/p&gt;\u0000 \u0000 &lt;p&gt;&lt;/p&gt;\u0000 &lt;/section&gt;\u0000 \u0000 &lt;section&gt;\u0000 \u0000 &lt;h3&gt; Key Scientists&lt;/h3&gt;\u0000 \u0000 &lt;p&gt;In 2011, Hayashi and Shintani reported a pioneering Pd-catalyzed asymmetric ring expansion of silacyclobutanes with alkynes, enabling the construction of cyc","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"44 10","pages":"1638-1656"},"PeriodicalIF":5.5,"publicationDate":"2026-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147696375","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}

{"title":"Enantioselective Construction of Diverse Tetrahydropyridazines via an Asymmetric [4+2] Annulation Reaction with α-Halogeno Hydrazones and Enecarbamates","authors":"Wei Li,&nbsp;Sen Wang,&nbsp;Zhifei Zhao,&nbsp;Jixing Zhao,&nbsp;Yanzhao Dong,&nbsp;Shi-Wu Li","doi":"10.1002/cjoc.70501","DOIUrl":"https://doi.org/10.1002/cjoc.70501","url":null,"abstract":"<div>\u0000 \u0000 <p>A highly efficient catalytic enantioselective [4+2] annulation reaction between acyclic or cyclic enecarbamates and <i>in situ</i>-generated azoalkenes (derived from α-halohydrazones) has been successfully realized using a Cu(I)/(4R,2R_p)-Ph-Phosferrox complex. Performed under mild reaction conditions, this robust synthetic protocol affords a structurally diverse collection of chiral tetrahydropyridazine derivatives bearing multiple contiguous stereogenic centers, with good to excellent isolated yields (48%–94%), high enantioselectivities up to 96% ee, and excellent diastereocontrol (dr &gt; 20 : 1). This reaction also exhibits outstanding substrate generality and tolerance, accommodating a wide scope of substituted α-halohydrazones and structurally varied enecarbamates, thereby enabling the facile construction of a diverse library of functionalized chiral tetrahydropyridazines. A gram-scale experiment and subsequent synthetic derivatizations of the chiral products were conducted to fully verify the practical utility and scalability of this catalytic system for potential synthetic applications. Single-crystal X-ray diffraction analysis of a representative product unambiguously confirmed its absolute configuration, and combined with systematic control experiments, these results clarified that the annulation proceeds through a stepwise [4+2] cycloaddition pathway. Additionally, comprehensive mechanistic studies including nonlinear effect assays, UV absorption spectroscopic analyses and Job's plot measurements were performed, which together provide solid experimental evidence to firmly validate the scientific rationality of the proposed reaction mechanism.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"44 10","pages":"1579-1590"},"PeriodicalIF":5.5,"publicationDate":"2026-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147696339","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}

{"title":"Palladium/PC-Phos-Catalyzed Enantioselective Dearomatization of Furfural N-Sulfonylhydrazones with Aryl Halides","authors":"Xinyue Wang,&nbsp;Chun Ma,&nbsp;Junfeng Yang,&nbsp;Junliang Zhang","doi":"10.1002/cjoc.70485","DOIUrl":"https://doi.org/10.1002/cjoc.70485","url":null,"abstract":"<div>\u0000 \u0000 <p>Spiroketals have gathered considerable attention owing to their prevalence in ligands, pharmaceuticals, and natural products. Their three-dimensional complexity often imparts desirable biological activity. Nevertheless, enantioselective synthesis of spiroketals still represents considerable challenges. Herein, we report a Pd/PC-Phos-catalyzed enantioselective nucleophilic dearomatization of furfural <i>N</i>-sulfonylhydrazones with readily available aryl halides. Up to 96.5 : 3.5 <i>er</i>, 99/1 <i>Z</i>/<i>E</i> and 73% yield have been achieved. Moreover, the reaction exhibits broad substrate compatibility, good functional group tolerance, easy scalability and versatile product functionalization. This protocol enables the synthesis of chiral spiroketals in high enantioselectivity and <i>Z</i>/<i>E</i> selectivity that have limited previous synthetic access. In addition, the origins of enantioselectivity were further rationalized using density functional theory calculations. The enantio-determining step is speculated to be the carbenation process.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"44 10","pages":"1557-1564"},"PeriodicalIF":5.5,"publicationDate":"2026-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147696340","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}