Journal of Catalysis最新文献

{"title":"Nickel-catalyzed amination of aryl halides: An exogenous ligand-free approach to primary arylamines using TMSN3","authors":"Jiawei Huang, Xiaoman Li, Zhigang Lei, Liang Xu, Shuai Liu","doi":"10.1016/j.jcat.2025.116284","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116284","url":null,"abstract":"Efficiently synthesizing primary amines continues to pose a significant challenge in the field of synthetic chemistry. This study reports a highly effective nickel-catalyzed amination of aryl halides using trimethylsilyl azide (TMSN₃) as the nitrogen source, facilitated by methoxytrimethylsilane (MeO₃SiH) under thermal conditions. Notably, this reaction proceeds without the need for an exogenous ligand and under mild conditions. Mechanistic investigations reveal that (MeO)₃SiH promotes the formation of Ni(I) species, which cycle through Ni(I)/Ni(III) intermediates, driving the amination process efficiently.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"26 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144329353","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":"O-(La)-promoted hydrogen transfer enables low-loading Pd catalysts for selective acetylene hydrogenation","authors":"Guandong Wu, Mengchen Yang, Yejiao Han, Yufei He, Dianqing Li","doi":"10.1016/j.jcat.2025.116286","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116286","url":null,"abstract":"The selective hydrogenation of acetylene using Pd-based catalysts is often limited by high precious metal usage and competitive adsorption between hydrogen and acetylene on active sites, which reduces catalytic efficiency. To address this, we developed a PdAg catalyst supported on La-doped Al₂O₃, introducing O-(La) sites that enhance hydrogen storage and transfer. In-situ Fourier Transform Infrared Spectroscopy (FTIR), temperature-programmed desorption (TPD), and mass spectrometry analyses revealed that the O-(La) sites enable efficient storage of dissociated hydrogen, which selectively reacts with acetylene, reducing competition on Pd sites. Density Functional Theory (DFT) calculations confirmed that the O-(La) sites reduce the energy barrier for hydrogen migration and enhance acetylene hydrogenation. This innovative approach reduces the Pd content by up to 30% while achieving superior catalytic performance, offering a cost-effective and scalable solution for industrial hydrogenation processes.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"4 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144329350","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":"Simultaneous removal of ethane and NOx over Ce-MnO2 catalysts: Insights into dual-functional mechanisms and temperature-dependent interactions","authors":"Shasha Du, Jiangliang Hu, Decheng Peng, Jiancheng Wang, Bing Wang, Weiren Bao, Jiayu Li, Liping Chang, Zhenping Qu","doi":"10.1016/j.jcat.2025.116281","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116281","url":null,"abstract":"Ce-<em>X</em>-MnO₂ (<em>X</em> = α, β, γ, δ) catalysts with four MnO₂ structures were synthesized for simultaneous ethane and NO_x removal. Ce-γ-MnO₂ exhibited the highest performance, achieving &gt; 80 % conversion for ethane (276 °C) and NO (120–330 °C). Various characterizations demonstrated a correlation between the activity and the abundance of Lewis acid-base pairs, with a higher amount of these species linked to better reactivity. The Mn⁴⁺-O-Ce sites were identified as active centers: ethane oxidation followed the MvK mechanism, while NH₃-SCR proceeded via both L-H and E-R pathways. The inhibition of ethane oxidation by NH₃-SCR reactants was primarily due to NH₃ suppressing ethane adsorption and competing for oxygen species. As ethane activation accelerated above 200 °C, NO₂ generated from NO oxidation tended to donate reactive oxygen, reconstructing the surface oxygen species and concurrently mitigating the NH₃ inhibition. Additionally, NO₂ dissociation released NO, further decreasing NO conversion at higher temperatures. Below 200 °C, new Lewis and Brønsted acid sites were generated during ethane activation, promoting NH₃ adsorption and improving low-temperature SCR activity.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"26 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144329347","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":"Photocatalytic cross-coupling of amines and alcohols over Au/TiO2: Reaction atmosphere-regulating imines and secondary amines synthesis","authors":"Yiwei Zhou, Jian Zhao, Hairui Guo, Cheng Wang","doi":"10.1016/j.jcat.2025.116288","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116288","url":null,"abstract":"The cross-coupling of alcohols with amines is an atomically efficient process for the synthesis of imines (C<img alt=\"double bond\" src=\"https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/55/entities/dbnd.gif\" style=\"vertical-align:middle\"/>N) and secondary amines (C<img alt=\"single bond\" src=\"https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/55/entities/sbnd.gif\" style=\"vertical-align:middle\"/>N), but developing efficient catalytic systems with C<img alt=\"double bond\" src=\"https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/55/entities/dbnd.gif\" style=\"vertical-align:middle\"/>N and C<img alt=\"single bond\" src=\"https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/55/entities/sbnd.gif\" style=\"vertical-align:middle\"/>N bonds precisely regulated under mild conditions remains a challenge. Here, utilizing the light as the only energy input, we achieved the efficient synthesis of imines and secondary amines by manipulating the hydrogen-transfer pathway over Au/TiO₂ with different reaction atmosphere. 100 % aniline conversion with 99 % secondary amine selectivity and 70 % aniline conversion with 99 % imine selectivity could be obtained, under N₂ and CO₂ atmosphere, respectively. Various control experiments and spectroscopies including <em>in situ</em> DRIFTS were tested. The investigations showed that UV-excited TiO₂ catalyzed the dehydrogenation of benzyl alcohol to produce hydrogen proton (H⁺), while the Au NPs catalyzed H⁺ reduction with the photogenerated electrons transferred from P25 to the interface of Au/TiO₂, forming Au-H species. The Au-H species hydrogenated imine to secondary amine in N₂ and the excellent hydrogen transfer capability of Au NPs was further proved compared with other metal counterparts. When replacing N₂ with CO₂, the CO intermediates derived from CO₂ reduction adsorbed on Au surface and inhibited the hydrogen transfer capability of the Au NPs, maintaining the C<img alt=\"double bond\" src=\"https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/55/entities/dbnd.gif\" style=\"vertical-align:middle\"/>N bonds. This work provides a new strategy for CO₂ utilization and for tuning the C<img alt=\"double bond\" src=\"https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/55/entities/dbnd.gif\" style=\"vertical-align:middle\"/>N and C<img alt=\"single bond\" src=\"https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/55/entities/sbnd.gif\" style=\"vertical-align:middle\"/>N bonds in photocatalytic organic transformations with Au-based catalyst.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"238 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144329355","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":"Modulating charge transfer dynamics in one-dimensional covalent organic frameworks for boosted photocatalytic H2 generation","authors":"Ruxue Wang, Zhongliao Wang, Lingling Li, Lijie Zhang, Jinfeng Zhang, Huile Jin, Quanlong Xu, Yuechang Wei, Yun Yang, Shun Wang","doi":"10.1016/j.jcat.2025.116289","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116289","url":null,"abstract":"Achieving strong dipole moment has been established as a promising strategy to improve the charge separation of nitrogen (N)-heterocycle-based covalent organic frameworks (COFs). However, the intrinsic polarization property causes weak π-electron delocalization and detrimentally affects the photocatalytic solar fuel generation. Herein, N-heterocycle-functionalized nonlinear <em>C₂</em> linkage with nonuniform N atom distribution was condensed with planar <em>C₄</em> knots to construct one-dimensional (1D) COFs, which possesses strong dipole moment, thus contributing efficient exciton dissociation and high charge carrier separation feature. Furthermore, a fully π-conjugated segment was simultaneously formed, serving as fast charge carrier transfer channel. As a result, the synthesized 1D COFs achieves a remarkable photocatalytic H₂ generation performance, and the aquantum efficiency (AQE) was detected to be 0.17 % at 420 nm. This work provides a general protocol for precisely modulating COF structure at molecular level to achieve high photocatalytic performance.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"607 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144329356","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":"Double-edged sword effect of seawater in CH4 photo-oxidation to CH3OOH: Boosting C–H activation while reducing peroxidation","authors":"Weixin Li, Wenhao Zhou, Yufei Cui, Hui Yang, Yongqing Ma, Ganhong Zheng, Chuhong Zhu, Meiling Wang","doi":"10.1016/j.jcat.2025.116291","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116291","url":null,"abstract":"Realizing methane (CH₄) direct converting to value-added liquid products with high selectivity still confronts huge challenges, particularly expensive catalyst costs and inferior catalyst stability. In this work, 0.6 M NaCl was firstly tentatively investigated for CH₄ conversion with presence of H₂O₂. Then renewable, scalable and economic seawater from the Yellow Sea is directly used for catalyzing CH₄ conversion to CH₃OOH, and it was found that seawater increased CH₃OOH production by fivefold (from 4.7–23.8 μmol h⁻¹), while reduced CO₂ production by four-fifths (from 37.0 %–7.4 %) during 8 h, demonstrating the double-edged sword effect of seawater: boosting C<img alt=\"single bond\" src=\"https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/55/entities/sbnd.gif\" style=\"vertical-align:middle\"/>H activation and reducing peroxidation. In addition, no performance degradation is observed at all during 8 h reaction, proving the good stability of seawater as catalyst for CH₄ conversion. Mechanism investigation indicates that in situ formed HOOCl play key roles in CH₄ activation and further conversion to CH₃OOH. This study highlights the effectiveness of seawater in energy conversion, which would bring huge economic benefits for the sustainable development and utilization of marine CH₄.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"14 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144329352","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":"Lithium nitride (Li3N) formation in lithium-mediated electrochemical ammonia synthesis can Be enhanced with the right proton donor","authors":"Victor Azumah, Lance Kavalsky, Venkatasubramanian Viswanathan","doi":"10.1016/j.jcat.2025.116250","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116250","url":null,"abstract":"Lithium-mediated electrochemical ammonia synthesis (LiMEAS) hinges on the formation of lithium nitride (Li&lt;sub&gt;3&lt;/sub&gt;N) from dissociated nitrogen at a lithium surface. Although proton donors (PDs) are known to influence nitrogen activation, their specific role in promoting Li&lt;sub&gt;3&lt;/sub&gt;N formation is still being investigated. Herein, we employ density functional theory (DFT) to examine the effects of 14 PDs on the stability and energetics of Li&lt;sub&gt;3&lt;/sub&gt;N formation. We show that in the absence of PD, Li&lt;sub&gt;3&lt;/sub&gt;N formation is consistently outcompeted by subsurface N&lt;sub&gt;2&lt;/sub&gt; embedding and, in some cases, by surface N&lt;sub&gt;2&lt;/sub&gt; adsorption. However, the introduction of PD species yields three distinct outcomes: (i) the PD remains intact during Li&lt;sub&gt;3&lt;/sub&gt;N formation, (ii) the PD protonates Li&lt;sub&gt;3&lt;/sub&gt;N, or (iii) the PD undergoes structural change. Notably, configurations in which the PD remains intact exhibited greater stability compared to subsurface embedding, driven by PD-induced surface reconstruction. We quantify this reconstruction using a two-layer displacement metric and find a strong correlation between the magnitude of displacement and the system’s overall stability. Further charge analyses show that the enhanced Li&lt;sub&gt;3&lt;/sub&gt;N stability correlates with a greater electron transfer to nitrogen. Finally, we link the basicity, acidity and polarity of PD with the results of the formation of nitride, demonstrating that the basicity of PD promotes intact configurations Li&lt;sub&gt;3&lt;/sub&gt;N. In contrast, higher acidity and polarity lead to protonation and alteration of PD. These insights pinpoint a region in the Kamlet–Taft &lt;span&gt;&lt;span style=\"\"&gt;&lt;/span&gt;&lt;span data-mathml='&lt;math xmlns=\"http://www.w3.org/1998/Math/MathML\"&gt;&lt;mi is=\"true\"&gt;&amp;#x3B2;&lt;/mi&gt;&lt;/math&gt;' role=\"presentation\" style=\"font-size: 90%; display: inline-block; position: relative;\" tabindex=\"0\"&gt;&lt;svg aria-hidden=\"true\" focusable=\"false\" height=\"2.432ex\" role=\"img\" style=\"vertical-align: -0.582ex;\" viewbox=\"0 -796.9 573.5 1047.3\" width=\"1.332ex\" xmlns:xlink=\"http://www.w3.org/1999/xlink\"&gt;&lt;g fill=\"currentColor\" stroke=\"currentColor\" stroke-width=\"0\" transform=\"matrix(1 0 0 -1 0 0)\"&gt;&lt;g is=\"true\"&gt;&lt;use xlink:href=\"#MJMATHI-3B2\"&gt;&lt;/use&gt;&lt;/g&gt;&lt;/g&gt;&lt;/svg&gt;&lt;span role=\"presentation\"&gt;&lt;math xmlns=\"http://www.w3.org/1998/Math/MathML\"&gt;&lt;mi is=\"true\"&gt;β&lt;/mi&gt;&lt;/math&gt;&lt;/span&gt;&lt;/span&gt;&lt;script type=\"math/mml\"&gt;&lt;math&gt;&lt;mi is=\"true\"&gt;β&lt;/mi&gt;&lt;/math&gt;&lt;/script&gt;&lt;/span&gt;–&lt;span&gt;&lt;span style=\"\"&gt;&lt;/span&gt;&lt;span data-mathml='&lt;math xmlns=\"http://www.w3.org/1998/Math/MathML\"&gt;&lt;mi is=\"true\"&gt;&amp;#x3C0;&lt;/mi&gt;&lt;/math&gt;' role=\"presentation\" style=\"font-size: 90%; display: inline-block; position: relative;\" tabindex=\"0\"&gt;&lt;svg aria-hidden=\"true\" focusable=\"false\" height=\"1.394ex\" role=\"img\" style=\"vertical-align: -0.235ex;\" viewbox=\"0 -498.8 573.5 600.2\" width=\"1.332ex\" xmlns:xlink=\"http://www.w3.org/1999/xlink\"&gt;&lt;g fill=\"currentColor\" stroke=\"currentColor\" stroke-width=\"0\" transform=\"matr","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"4 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144312173","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":"Conversion of furfuryl alcohol to 1,5-pentanediol over tetrametallic Cu/CoOx/MgO/Al2O3 mixed metal oxide catalyst","authors":"Asier Barredo, Ane Bueno, Nerea Viar, Jesús M. Requies, Inaki Gandarias","doi":"10.1016/j.jcat.2025.116283","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116283","url":null,"abstract":"The hydrogenolysis of furfuryl alcohol to 1,5-pentanediol is investigated over a tetrametallic Cu/CoO_x/MgO/Al₂O₃ catalytic system. Activity and characterization results suggested the specific roles of each metal: Cu⁰ dissociates H₂, whereas CoO_x, as a reducible oxide, generates Co^δ+ sites next to oxygen vacancies where furfuryl alcohol adsorbs. Activated hydrogen spills over from Cu⁰ to these coordinatively unsaturated Co^δ+ sites, enabling the hydrogenolysis of furfuryl alcohol to 1,5-pentanediol. Furthermore, Cu⁰ aids in the reduction of Co oxide species at lower temperatures during the catalyst activation, thereby promoting the generation of uncoordinated Co^δ+ sites. The presence of MgO decreases overall acidity, resulting in reduced hydrogenolysis of furfuryl alcohol to 2-methylfuran and increased selectivity towards 1,5-pentanediol. Finally, the presence of Al₂O₃ in the catalyst enhances metal dispersion reducing the furanic ring hydrogenation to yield tetrahydrofurfuryl alcohol. With the optimized catalyst, a 43.8 % 1,5-pentanediol yield is obtained at 160 °C for 4 h in ethanol, achieving a TOF of 27.4 mol_1,5-PDO mol⁻¹_A.S. h⁻¹.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"234 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144312175","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":"Accessing tetrasubstituted alkenes by co-catalyzed stereoselective hydrosilylation of 2,3-disubstituted 1,2-dienes","authors":"Ziwei Luo,&nbsp;Hao Zeng,&nbsp;Junyang Cen,&nbsp;Ze Li,&nbsp;Guo-Qiao Lai,&nbsp;Pinglu Zhang","doi":"10.1016/j.jcat.2025.116278","DOIUrl":"10.1016/j.jcat.2025.116278","url":null,"abstract":"<div><div>Tetrasubstituted alkene frameworks have been extensively employed in pharmaceuticals and material science, while their synthesis is of great challenging due to the uncontrolled <em>Z/E</em> selectivity. Here we would like to provide a novel and robust strategy to access a variety of tetrasubstituted alkenes via a cobalt-catalyzed stereoselective hydrosilylation of 2,3-disubstituted dienes. This study would like to provide a novel platform for fulfilling the map in construction of tetrasubstituted alkenes.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116278"},"PeriodicalIF":6.5,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305141","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 synthesis of δ-Boryl chiral amines/amides via copper-catalyzed sequential hydroboration hydroamination/hydroaminocarbonylation of methylenecyclopropanes","authors":"Yang Yuan ,&nbsp;Fangbei Ge ,&nbsp;Ting Yang ,&nbsp;Xiao-Feng Wu","doi":"10.1016/j.jcat.2025.116280","DOIUrl":"10.1016/j.jcat.2025.116280","url":null,"abstract":"<div><div>We report the development of a copper-catalyzed asymmetric synthesis of δ-boryl chiral amines and amides via sequential ring-opening reactions of methylenecyclopropanes (MCPs). Using Cu(OAc)₂ /(<em>R</em>)-DTBM-Segphos catalytic system, MCPs undergo hydroboration-hydroamination with HBpin and hydroxylamine esters to produce δ-boryl chiral amines in good yields (up to 85 %) and excellent enantioselectivities (up to &gt;99 % ee). The method shows broad substrate scope, tolerating various functional groups and structural motifs. Additionally, CuCl/(<em>S</em>,<em>S</em>)-Ph-BPE enables sequential hydroboration-hydroaminocarbonylation of MCPs under CO atmosphere, affording δ-boryl chiral amides with high enantioselectivity (up to 99 % ee). The synthetic utility of these methods is highlighted through various stereospecific transformations of the products. Mechanistic studies indicate that these transformations proceed via copper-catalyzed ring-opening hydroboration to form homoallylic boronate intermediates, followed by enantioselective hydroamination or hydroaminocarbonylation steps to produce the final δ-boryl chiral amines and amides.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116280"},"PeriodicalIF":6.5,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144278998","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}