ACS Combinatorial Science最新文献

Ligand-Enabled Cu-Catalyzed Stereoselective Synthesis of P-Stereogenic ProTides 配体催化的铜催化立体选择性合成 P-Stereogenic ProTides

IF 14.4 3区化学

ACS Combinatorial Science Pub Date : 2024-11-04 DOI: 10.1021/jacs.4c1292010.1021/jacs.4c12920

Shuai-Shuai Fang, XiangJun Hu, Ming-Hong Li, Shuang Qi, Tian Xie, Jia-Bao Wang, Hong-Qing Yao, Jian Zhang, Jun-Hua Zhang*, Lijuan Zhu* and Ming Shang*,

{"title":"Ligand-Enabled Cu-Catalyzed Stereoselective Synthesis of P-Stereogenic ProTides","authors":"Shuai-Shuai Fang, XiangJun Hu, Ming-Hong Li, Shuang Qi, Tian Xie, Jia-Bao Wang, Hong-Qing Yao, Jian Zhang, Jun-Hua Zhang*, Lijuan Zhu* and Ming Shang*, ","doi":"10.1021/jacs.4c1292010.1021/jacs.4c12920","DOIUrl":"https://doi.org/10.1021/jacs.4c12920https://doi.org/10.1021/jacs.4c12920","url":null,"abstract":"Nucleoside analogues have seen significant advancements in treating viral infections and cancer through ProTide technology, leading to a series of FDA-approved drugs such as sofosbuvir, tenofovir alafenamide, and remdesivir. The stereochemical configuration at the phosphorus center of ProTides significantly influences their pharmacological properties, necessitating efficient stereoselective synthesis. Traditional methods using chiral auxiliaries or nonracemic phosphorylating agents are labor-intensive and inefficient, while recent organocatalytic approaches, despite their promise, still face limitations. Herein, we present a novel approach employing chiral metal complexes for the stereoselective assembly of P-stereogenic ProTides via asymmetric P–O bond formation. This approach leverages a chiral metal catalyst to activate the electrophilic phosphorylating reagent, facilitating a base-promoted nucleophilic replacement pathway. Our protocol, featuring mild reaction conditions and broad applicability, enables the highly stereoselective synthesis of previously inaccessible (S,RP) and (R,SP)-ProTide derivatives. The practical utility of this method is demonstrated through the preparation of pharmaceutically relevant ProTide targets and mechanistic studies were conducted to elucidate the reaction pathway, offering significant advancements for drug development and pharmaceutical research.","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 45","pages":"31339–31347 31339–31347"},"PeriodicalIF":14.4,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142608015","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Aziridine Group Transfer via Transient N-Aziridinyl Radicals 通过瞬时 N-氮丙啶自由基转移氮丙啶基团

IF 14.4 3区化学

ACS Combinatorial Science Pub Date : 2024-11-04 DOI: 10.1021/jacs.4c1416910.1021/jacs.4c14169

Promita Biswas, Asim Maity, Matthew T. Figgins and David C. Powers*,

引用次数: 0

Difluorocarbene Generation via a Spin-Forbidden Excitation under Visible Light Irradiation 在可见光照射下通过自旋禁激生成二氟碳化合物

IF 14.4 3区化学

ACS Combinatorial Science Pub Date : 2024-11-04 DOI: 10.1021/jacs.4c1093910.1021/jacs.4c10939

Shan Liu, Guang-Ning Pan, Yijing Ling, Feng Gao, Yin Yang, Ganglong Cui*, Qilong Shen* and Tianfei Liu*,

{"title":"Difluorocarbene Generation via a Spin-Forbidden Excitation under Visible Light Irradiation","authors":"Shan Liu, Guang-Ning Pan, Yijing Ling, Feng Gao, Yin Yang, Ganglong Cui*, Qilong Shen* and Tianfei Liu*, ","doi":"10.1021/jacs.4c1093910.1021/jacs.4c10939","DOIUrl":"https://doi.org/10.1021/jacs.4c10939https://doi.org/10.1021/jacs.4c10939","url":null,"abstract":"The generation of difluorocarbene from difluoromethane bis(sulfonium ylide) 1 through spin-forbidden excitation under irradiation with 450 nm blue light was reported. The formation of difluorocarbene was confirmed by its reaction with styrene derivatives for the generation of difluorocyclopropanation and insertion into RX–H bonds (X = O, S) for the generation of RXCF2H. The spin-forbidden excitation mechanism for the formation of difluorocarbene from difluoromethane bis(sulfonium ylide) was supported by spectroscopic and kinetic studies as well as computational chemistry. The homolytic cleavage of two S–C bonds in compound 1 under irradiation was confirmed by time-resolved EPR spectroscopic studies of the precursor’s free-radical-capturing reaction, as well as the isolation of the dimer of dimethyl (phenylthiol)malonyl radical. Further studies showed that the homolytic cleavage process occurred asynchronously in the solvent cage based on the isotope-labeled scrambling experiments and DFT calculations.","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 45","pages":"31094–31105 31094–31105"},"PeriodicalIF":14.4,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142608071","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Electrochemical Synthesis of Nitrite and Nitrate via Cathodic Oxygen Activation in Liquefied Ammonia 在液化氨中通过阴极氧活化电化学合成亚硝酸盐和硝酸盐

IF 14.4 3区化学

ACS Combinatorial Science Pub Date : 2024-11-04 DOI: 10.1021/jacs.4c1027910.1021/jacs.4c10279

Moritz Lukas Krebs, and , Ferdi Schüth*,

引用次数: 0

Molecular Synergistic Effects Mediate Efficient Interfacial Chemistry: Enabling Dendrite-Free Zinc Anode for Aqueous Zinc-Ion Batteries 分子协同效应介导高效界面化学：实现锌离子水电池的无枝晶锌阳极

IF 14.4 3区化学

ACS Combinatorial Science Pub Date : 2024-11-04 DOI: 10.1021/jacs.4c1033710.1021/jacs.4c10337

Yue-Ming Li, Wen-Hao Li, Kai Li, Wen-Bin Jiang, Yuan-Zheng Tang, Xiao-Ying Zhang, Hai-Yan Yuan*, Jing-Ping Zhang* and Xing-Long Wu*,

{"title":"Molecular Synergistic Effects Mediate Efficient Interfacial Chemistry: Enabling Dendrite-Free Zinc Anode for Aqueous Zinc-Ion Batteries","authors":"Yue-Ming Li, Wen-Hao Li, Kai Li, Wen-Bin Jiang, Yuan-Zheng Tang, Xiao-Ying Zhang, Hai-Yan Yuan*, Jing-Ping Zhang* and Xing-Long Wu*, ","doi":"10.1021/jacs.4c1033710.1021/jacs.4c10337","DOIUrl":"https://doi.org/10.1021/jacs.4c10337https://doi.org/10.1021/jacs.4c10337","url":null,"abstract":"The primary cause of the accelerated battery failure in aqueous zinc-ion batteries (AZIBs) is the uncontrollable evolution of the zinc metal–electrolyte interface. In the present research on the development of multiadditives to ameliorate interfaces, it is challenging to elucidate the mechanisms of the various components. Additionally, the synergy among additive molecules is frequently disregarded, resulting in the combined efficacy of multiadditives that is unlikely to surpass the sum of each component. In this study, the “molecular synergistic effect” is employed, which is generated by two nonhomologous acid ester (NAE) additives in the double electrical layer microspace. Specifically, ethyl methyl carbonate (EMC) is more inclined to induce the oriented deposition of zinc metal by means of targeted adsorption with the zinc (002) crystal plane. Methyl acetate (MA) is more likely to enter the solvated shell of Zn2+ and will be profoundly reduced to produce SEI that is dominated by organic components under the “molecular synergistic effect” of EMC. Furthermore, MA persists in a spontaneous hydrolysis reaction, which serves to mitigate the pH increase caused by the hydrogen evolution reaction (HER) and further prevents the formation of byproducts. Consequently, the 1E1M electrolyte not only extends the cycle life of the zinc anode to 3140 cycles (1 mA h cm–2 and 1 mA cm–2) but also extends the life of the Zn//MnO2 full battery, with the capacity retention rate still at 89.9% after 700 cycles.","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 45","pages":"30998–31011 30998–31011"},"PeriodicalIF":14.4,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142608054","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Continuous Electrosynthesis of Pure H2O2 Solution with Medical-Grade Concentration by a Conductive Ni-Phthalocyanine-Based Covalent Organic Framework 利用导电性镍酞菁共价有机框架连续电合成医用级浓度的纯 H2O2 溶液

IF 14.4 3区化学

ACS Combinatorial Science Pub Date : 2024-11-04 DOI: 10.1021/jacs.4c1067510.1021/jacs.4c10675

Meng-Di Zhang, Jia-Run Huang, Cheng-Peng Liang, Xiao-Ming Chen and Pei-Qin Liao*,

{"title":"Continuous Electrosynthesis of Pure H2O2 Solution with Medical-Grade Concentration by a Conductive Ni-Phthalocyanine-Based Covalent Organic Framework","authors":"Meng-Di Zhang, Jia-Run Huang, Cheng-Peng Liang, Xiao-Ming Chen and Pei-Qin Liao*, ","doi":"10.1021/jacs.4c1067510.1021/jacs.4c10675","DOIUrl":"https://doi.org/10.1021/jacs.4c10675https://doi.org/10.1021/jacs.4c10675","url":null,"abstract":"Electrosynthesis of H2O2 provides an environmentally friendly alternative to the traditional anthraquinone method employed in industry, but suffers from impurities and restricted yield rate and concentration of H2O2. Herein, we demonstrated a Ni-phthalocyanine-based covalent-organic framework (COF, denoted as BBL-PcNi) with a higher inherent conductivity of 1.14 × 10–5 S m–1, which exhibited an ultrahigh current density of 530 mA cm–2 with a Faradaic efficiency (H2O2) of ∼100% at a low cell voltage of 3.5 V. Notably, this high level of performance is maintained over a continuous operation of 200 h without noticeable degradation. When integrated into a scale-up membrane electrode assembly electrolyzer and operated at ∼3300 mA at a very low cell voltage of 2 V, BBL-PcNi continuously yielded a pure H2O2 solution with medical-grade concentration (3.5 wt %), which is at least 3.5 times higher than previously reported catalysts and 1.5 times the output of the traditional anthraquinone process. A mechanistic study revealed that enhancing the π-conjugation to reduce the band gap of the molecular catalytic sites integrated into a COF is more effective to enhance its inherent electron transport ability, thereby significantly improving the electrocatalytic performance for H2O2 generation.","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 45","pages":"31034–31041 31034–31041"},"PeriodicalIF":14.4,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142608069","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Antiaromatic Metallacyclopentatriene Complexes 反芳香族金属杂环戊三烯络合物

IF 14.4 3区化学

ACS Combinatorial Science Pub Date : 2024-11-04 DOI: 10.1021/jacs.4c1414110.1021/jacs.4c14141

Bingjie Fu, Yarong Wang, Yue Zhao, Yang Li*, Wenfeng Jiang* and Wei Bai*,

引用次数: 0

Syntheses, Geometric and Electronic Structures of Inorganic Cumulenes 无机积雪烯的合成、几何结构和电子结构

IF 14.4 3区化学

ACS Combinatorial Science Pub Date : 2024-11-04 DOI: 10.1021/jacs.4c1323110.1021/jacs.4c13231

Jianqin Tang, Chenyang Hu, Agamemnon E. Crumpton, Maximilian Dietz, Debotra Sarkar, Liam P. Griffin, Jose M. Goicoechea* and Simon Aldridge*,

{"title":"Syntheses, Geometric and Electronic Structures of Inorganic Cumulenes","authors":"Jianqin Tang, Chenyang Hu, Agamemnon E. Crumpton, Maximilian Dietz, Debotra Sarkar, Liam P. Griffin, Jose M. Goicoechea* and Simon Aldridge*, ","doi":"10.1021/jacs.4c1323110.1021/jacs.4c13231","DOIUrl":"https://doi.org/10.1021/jacs.4c13231https://doi.org/10.1021/jacs.4c13231","url":null,"abstract":"Molecular chains of two-coordinate carbon atoms (cumulenes) have long been targeted, due to interest in the electronic structure and applications of extended π-systems, and their relationship to the carbon allotrope, carbyne. While formal (isoelectronic) B═N for C═C substitution has been employed in two-dimensional (2-D) materials, unsaturated one-dimensional all-inorganic “molecular wires” are unknown. Here, we report high-yielding synthetic approaches to heterocumulenes containing a five-atom BNBNB chain, the geometric structure of which can be modified by choice of end group. The diamido-capped system is bent at the 2-/4-positions, and natural resonance theory calculations reveal significant contributions from B═N(:)–B≡N–B resonance forms featuring a lone pair at N (consistent with observed N-centered nucleophilicity). Molecular modification to generate a linear system best described by a B═N═B═N═B resonance structure involves chemical transformation of the capping groups (using B(C5F5)3) to enhance their π-acidity and conjugate the N-lone pairs.","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 45","pages":"30778–30783 30778–30783"},"PeriodicalIF":14.4,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacs.4c13231","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142608279","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Double-Bridging Increases the Stability of Zinc(II) Metal–Organic Cages 双桥增加锌（II）金属有机笼的稳定性

IF 14.4 3区化学

ACS Combinatorial Science Pub Date : 2024-11-04 DOI: 10.1021/jacs.4c0974210.1021/jacs.4c09742

Hannah Kurz, Paula C. P. Teeuwen, Tanya K. Ronson, Jack B. Hoffman, Philipp Pracht, David J. Wales and Jonathan R. Nitschke*,

{"title":"Double-Bridging Increases the Stability of Zinc(II) Metal–Organic Cages","authors":"Hannah Kurz, Paula C. P. Teeuwen, Tanya K. Ronson, Jack B. Hoffman, Philipp Pracht, David J. Wales and Jonathan R. Nitschke*, ","doi":"10.1021/jacs.4c0974210.1021/jacs.4c09742","DOIUrl":"https://doi.org/10.1021/jacs.4c09742https://doi.org/10.1021/jacs.4c09742","url":null,"abstract":"A key feature of coordination cages is the dynamic nature of their coordinative bonds, which facilitates the synthesis of complex polyhedral structures and their post-assembly modification. However, this dynamic nature can limit cage stability. Increasing cage robustness is important for real-world use cases. Here we introduce a double-bridging strategy to increase cage stability, where designed pairs of bifunctional subcomponents combine to generate rectangular tetratopic ligands within pseudo-cubic Zn8L6 cages. These cages withstand transmetalation, the addition of competing ligands, and nucleophilic imines, under conditions where their single-bridged congeners decompose. Our approach not only increases the stability and robustness of the cages while maintaining their polyhedral structure, but also enables the incorporation of additional functional units in proximity to the cavity. The double-bridging strategy also facilitates the synthesis of larger cages, which are inaccessible as single-bridged congeners.","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 45","pages":"30958–30965 30958–30965"},"PeriodicalIF":14.4,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacs.4c09742","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142608055","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Constructing Flexible Crystalline Porous Organic Salts via a Zwitterionic Strategy 通过齐聚物策略构建柔性多孔有机盐晶体

IF 14.4 3区化学

ACS Combinatorial Science Pub Date : 2024-11-04 DOI: 10.1021/jacs.4c1071310.1021/jacs.4c10713

Jin Wang, Shengyi Yang, Liang Zhang, Xuedong Xiao, Zihao Deng, Xinmeng Chen, Cheng Liu, Gongyue Huang*, Ryan T. K. Kwok*, Jacky W. Y. Lam* and Ben Zhong Tang*,

{"title":"Constructing Flexible Crystalline Porous Organic Salts via a Zwitterionic Strategy","authors":"Jin Wang, Shengyi Yang, Liang Zhang, Xuedong Xiao, Zihao Deng, Xinmeng Chen, Cheng Liu, Gongyue Huang*, Ryan T. K. Kwok*, Jacky W. Y. Lam* and Ben Zhong Tang*, ","doi":"10.1021/jacs.4c1071310.1021/jacs.4c10713","DOIUrl":"https://doi.org/10.1021/jacs.4c10713https://doi.org/10.1021/jacs.4c10713","url":null,"abstract":"The unique ionic channels and highly polar pore structures have distinguished crystalline porous organic salts (CPOSs) from conventional porous frameworks in the past decade. Up to now, CPOSs were all constructed by a monoionic strategy, in which two types of building units individually bearing anionic or cationic groups were introduced, thus increasing complexity in the synthesis of CPOSs. In this study, by utilizing stereoisomeric compounds of TPE-NS-Z or TPE-NS-E bearing both anionic and cationic groups as a single building unit, the zwitterionic strategy was proven feasible in constructing CPOSs. Benefiting from the single building unit, the zwitterionic strategy simplified the preparation process and reduced the difficulty in studying the aggregation behavior of building units into CPOSs. And also, this novel strategy enabled precise control of the finally obtained CPOSs through fine-tuning of the initial building units. Surprisingly, the special parallel/vertical alternated stacking mode and unique ionic interaction networks in the crystal structure provided the flexible pore characteristic of CPOS-E, which further guaranteed the multitime controllable release of highly polar chemicals in different solvents.","PeriodicalId":14,"journal":{"name":"ACS Combinatorial Science","volume":"146 45","pages":"31042–31052 31042–31052"},"PeriodicalIF":14.4,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142608070","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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