Angewandte Chemie最新文献_第5页

Organocatalytic Enantioselective [4 + 4] Cycloadditions of Furan Ortho-Quinodimethanes 呋喃邻醌二甲烷的有机催化对映选择性[4 + 4]环加成反应

Angewandte Chemie Pub Date : 2025-08-29 DOI: 10.1002/ange.202514300

Dr. Niklas Lawaetz Østergaard, Anne Kristensen, Dr. Enrico Marcantonio, Mette Louise Skipper, Michał Dudziński, Dr. David A. McLeod, Prof. Dr. Karl Anker Jørgensen

{"title":"Organocatalytic Enantioselective [4 + 4] Cycloadditions of Furan Ortho-Quinodimethanes","authors":"Dr. Niklas Lawaetz Østergaard, Anne Kristensen, Dr. Enrico Marcantonio, Mette Louise Skipper, Michał Dudziński, Dr. David A. McLeod, Prof. Dr. Karl Anker Jørgensen","doi":"10.1002/ange.202514300","DOIUrl":"https://doi.org/10.1002/ange.202514300","url":null,"abstract":"The enantioselective [4 + 4] cycloaddition for the construction of cyclooctanoids is a challenging transformation in organic chemistry. Herein, we present the first organocatalytic enantioselective [4 + 4] cycloaddition of furan ortho-quinodimethanes, activated by dearomatization of the heteroaromatic compound, which thereby allows for the cycloaddition with dienes. The [4 + 4] cycloaddition is catalyzed by a quinine-derived primary amine in combination with a chiral phosphoric acid and a carboxylic acid affording cyclooctanoids isolated as a single diastereoisomer in good yields and with up to 94% ee. This reaction concept allows for the formation of cyclooctanoids without benzofusion, as demonstrated by oxidative opening of the furan ring. Computational studies of the reaction mechanism for the [4 + 4] cycloaddition point to a stepwise process. Surprisingly, the stereochemical outcome of the reaction is attributed to protonation of the two organocatalyst-bound cyclooctanoid intermediates leading to a preferred set-up for catalyst elimination to account for the absolute configuration of the cyclooctanoid.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 41","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202514300","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145230886","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Photocatalytic Formamide Synthesis from Plastic Waste and Ammonia via C─N Bond Construction Under Mild Conditions 温和条件下C─N键构建光催化废塑料和氨合成甲酰胺

Angewandte Chemie Pub Date : 2025-08-29 DOI: 10.1002/ange.202513991

Dr. Fulai Liu, Yifei Liang, Xin Zhao, Dr. Rui Shi, Prof. Dr. Chuanjun Wang, Prof. Dr. Yong Chen

{"title":"Photocatalytic Formamide Synthesis from Plastic Waste and Ammonia via C─N Bond Construction Under Mild Conditions","authors":"Dr. Fulai Liu, Yifei Liang, Xin Zhao, Dr. Rui Shi, Prof. Dr. Chuanjun Wang, Prof. Dr. Yong Chen","doi":"10.1002/ange.202513991","DOIUrl":"https://doi.org/10.1002/ange.202513991","url":null,"abstract":"Photocatalytic upcycling of polyethylene terephthalate (PET) waste into value-added chemicals represents a sustainable route for plastic valorization. However, previous studies have solely focused on generating oxygenated compounds through intramolecular C─O bond transformations. Achieving heteroatom-containing important chemicals via intermolecular coupling reactions is still challenging. Herein, we report the first example of the direct photocatalytic C─N coupling of PET-derived ethylene glycol (EG) with ammonia to produce formamide (FA) and H2 over a Pt1Au/TiO2 catalyst. Pt1Au/TiO2 delivers a FA yield rate of ∼7.1 mmol gcat−1 h−1, as well as H2 evolution (∼22.8 mmol gcat−1 h−1). Photoelectrochemical analyses, including time-resolved transient absorption spectroscopy (TAS) and in situ X-ray photoelectron spectroscopy (XPS), reveal that monatomic Pt sites can effectively trap electrons, while Au nanoparticles act as hole sinks, thereby synergistically enhancing charge separation efficiency. Mechanistic investigations via in situ electron paramagnetic resonance (EPR) and Fourier transform infrared spectroscopy (FTIR) elucidate the reaction pathway: EG undergoes hole-mediated oxidation to yield an aldehyde intermediate, which is subsequently attacked nucleophilically by hole-derived •NH2, inducing sequential C─C bond cleavage and C─N bond formation. This work provides critical mechanistic insights for the sustainable synthesis of high-value heteroatom-containing chemicals from plastic waste.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 41","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145230885","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

The Discovery and Development of an Iridium-Catalyzed N→C Alkyl Transfer Reaction 铱催化N→C烷基转移反应的发现与发展

Angewandte Chemie Pub Date : 2025-08-28 DOI: 10.1002/ange.202509193

Dr. Erin C. Boddie, Dr. Phillippa Cooper, Dr. L. Anders Hammarback, Dr. Richard J. Mudd, Lyman J. Feron, Prof. John F. Bower

引用次数: 0

Cell-Active, Irreversible Covalent Inhibitors Targeting a Surface-Exposed Non-Catalytic Lysine on Aurora a Kinase by Using Squarate Chemistry 细胞活性，不可逆的共价抑制剂，靶向表面暴露的非催化赖氨酸的极光激酶

Angewandte Chemie Pub Date : 2025-08-28 DOI: 10.1002/ange.202510763

Zuqin Wang, Xuan Wang, Yong Li, Peishan Li, Shengjie Huang, Peng Chen, Guanghui Tang, Xiaotong Ding, Prof. Dr. Zhang Zhang, Prof. Dr. Zhi-Min Zhang, Prof. Dr. Yang Zhou, Prof. Dr. Shao Q. Yao, Prof. Dr. Xiaoyun Lu

{"title":"Cell-Active, Irreversible Covalent Inhibitors Targeting a Surface-Exposed Non-Catalytic Lysine on Aurora a Kinase by Using Squarate Chemistry","authors":"Zuqin Wang, Xuan Wang, Yong Li, Peishan Li, Shengjie Huang, Peng Chen, Guanghui Tang, Xiaotong Ding, Prof. Dr. Zhang Zhang, Prof. Dr. Zhi-Min Zhang, Prof. Dr. Yang Zhou, Prof. Dr. Shao Q. Yao, Prof. Dr. Xiaoyun Lu","doi":"10.1002/ange.202510763","DOIUrl":"https://doi.org/10.1002/ange.202510763","url":null,"abstract":"Targeting surface-exposed lysines in kinases through covalent modification presents a major challenge due to their high pKa and inherently low reactivity. While current research primarily targets more reactive catalytic lysines buried in the ATP-binding pocket, no systematic rational strategy has yet been developed for selectively engaging surface-exposed lysines. Herein, we present a versatile strategy for developing cell-active covalent kinase inhibitors (CKIs) by selectively targeting unique surface-exposed lysines using squarate chemistry. By using Aurora A (AURKA) as a proof-of-concept, we systematically evaluated this approach against other well-known lysine-reactive warheads (e.g., EBA, SO2F, and OSO2F) and demonstrated, for the first time, squarates’ superior efficacy in engaging these challenging low-reactivity lysines. Amongst various AURKA CKIs, AL8 emerged as the first-in-class squarate-based, cell-active inhibitor, exhibiting excellent selectivity in both biochemical and cellular assays with long-residence time in covalently engaging endogenous AURKA. Detailed investigation of effects of leaving groups on squaric esters provided valuable insights for future development of lysine-reactive CKIs. Our finding has established squarate-containing ligands as a unique and readily tunable platform for covalent modification of surface-exposed, non-catalytic lysines in targeted kinase drug discovery.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 40","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145172049","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Regioselective Separation and Extraction of Polyalkylthiophene by Metal–Organic Frameworks 金属-有机骨架对聚烷基噻吩的区域选择性分离与萃取

Angewandte Chemie Pub Date : 2025-08-27 DOI: 10.1002/ange.202513518

Yu Takashima, Taku Sawayama, Dr. Nobuhiko Hosono, Prof. Takashi Uemura

引用次数: 0

Phospholipid-Drug Conjugates Self-Organized into Well-Defined Supramolecular Nanotubes for Efficient Drug Delivery 磷脂-药物缀合物自组织成定义良好的超分子纳米管，用于有效的药物递送

Angewandte Chemie Pub Date : 2025-08-27 DOI: 10.1002/ange.202509799

Zhiguo Gao, Wei He, Ke Qin, Jiaqi Xing, Yi Liang, Yinan Zhang, Baiwang Sun, Ran Mo

引用次数: 0

Rapid and Modular Access to All-Carbon Quaternary Center-Containing 2,2-Disubstituted Bicyclo[1.1.1]pentanes via Cyanocarbene Addition to Bicyclo[1.1.0]butanes 含2,2-二取代双环[1.1.1]戊烷的氰化羰基加成法快速模块化制备含全碳季中心的二环[1.1.1]戊烷

Angewandte Chemie Pub Date : 2025-08-27 DOI: 10.1002/ange.202513768

Xin-Yu Gao, Yuanjiu Xiao, Quanxin Peng, Fujian Yang, Daojing Li, Prof. Dr. Guoqiang Wang, Prof. Dr. Yu Qian, Prof. Dr. Jian-Jun Feng

{"title":"Rapid and Modular Access to All-Carbon Quaternary Center-Containing 2,2-Disubstituted Bicyclo[1.1.1]pentanes via Cyanocarbene Addition to Bicyclo[1.1.0]butanes","authors":"Xin-Yu Gao, Yuanjiu Xiao, Quanxin Peng, Fujian Yang, Daojing Li, Prof. Dr. Guoqiang Wang, Prof. Dr. Yu Qian, Prof. Dr. Jian-Jun Feng","doi":"10.1002/ange.202513768","DOIUrl":"https://doi.org/10.1002/ange.202513768","url":null,"abstract":"While 1,3-disubstituted bicyclo[1.1.1]pentanes (BCPs) have garnered considerable interest in medicinal chemistry as bioisosteres of para-substituted benzenes, the utilization of bridge-functionalized BCPs, especially those containing all-carbon quaternary centers at the bridge-positions, in drug design has lagged behind. This is primarily due to the synthetic challenges associated with these scaffolds. Herein, we report the insertion of diazo-free donor-acceptor carbenes into the C─C bond of bicyclo[1.1.0]butanes (BCBs), enabling the rapid and modular synthesis of 1,2,2,3-tetrasubstituted bicyclo[1.1.1]pentanes (BCPs) bearing three all-carbon quaternary centers in up to 83% yield. This transformation is metal-free, one-pot, operationally simple, and accomodates to a wide range of substrates. The decoration of bioactive molecules with 2,2-disubstituted BCP exhibits superior antitumor activity compared to the anticancer drug Sonidegib, rendering this method highly practical and appealing. Density functional theory (DFT) calculations combined with control experiments reveal that the reaction proceeds through a stepwise nucleophilic ring-opening/recyclization pathway, involving the reaction between the singlet carbene species and the BCB skeleton.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 41","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145230830","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Umpolung Activation of Bicyclobutanes via N-Heterocyclic Carbene Catalysis n -杂环卡宾催化双丁烷的非均匀活化

Angewandte Chemie Pub Date : 2025-08-27 DOI: 10.1002/ange.202513913

Yu-Che Chang, Renyu Guo, Thomas Fessard, Quentin Lefebvre, Christophe Salome, Prof. M. Kevin Brown

引用次数: 0

Dynamic Molecular Triplet Excitons Tune Lanthanide Emission Lifetime 动态分子三重态激子调谐镧系元素发射寿命

Angewandte Chemie Pub Date : 2025-08-26 DOI: 10.1002/ange.202513236

Takuma Nakai, Kaori Shima, Dr. Mengfei Wang, Dr. Sunao Shoji, Dr. Takayuki Nakanishi, Dr. Koji Fushimi, Dr. Yasuchika Hasegawa, Dr. Yuichi Kitagawa

{"title":"Dynamic Molecular Triplet Excitons Tune Lanthanide Emission Lifetime","authors":"Takuma Nakai, Kaori Shima, Dr. Mengfei Wang, Dr. Sunao Shoji, Dr. Takayuki Nakanishi, Dr. Koji Fushimi, Dr. Yasuchika Hasegawa, Dr. Yuichi Kitagawa","doi":"10.1002/ange.202513236","DOIUrl":"https://doi.org/10.1002/ange.202513236","url":null,"abstract":"Optical codes generated from the emission lifetimes of lanthanide complexes have received considerable attention for their potential application in multiplexed bioimaging and anti-counterfeiting. However, such tunable lifetimes are limited to short ranges (0.01−1 ms). Herein, we describe a method that extends the emission lifetime using dynamic molecular triplet excitons in aggregation systems composed of lanthanide complexes. To demonstrate the conceptual method, molecular crystals comprising lutetium (Lu3+) and luminescent lanthanide (europium: Eu3+ or terbium: Tb3+) complexes with two organic ligands (2,2,6,6-tetramethyl-3,5-heptanedionate and 2,7-bis(diphenylphosphoryl)phenanthrene) were prepared. These molecular crystals exhibited persistent emission via slow triplet exciton migration between the phenanthrene units. The extended degree of the lifetime could be controlled between 1 and 152 ms by ligand modifications. This proposed lifetime-tuning method should significantly expand the encoding capacity of lanthanide complexes.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 41","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145230736","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Iridium-Catalyzed Reductive Deoxygenation of Esters for the Synthesis of Sterically Hindered Ethers 铱催化酯的还原脱氧合成位阻醚

Angewandte Chemie Pub Date : 2025-08-26 DOI: 10.1002/ange.202508301

Dr. Yaseen A. Almehmadi, Anna J. Passmore, Dr. Pablo Gabriel, Prof. Dr. Darren J. Dixon

{"title":"Iridium-Catalyzed Reductive Deoxygenation of Esters for the Synthesis of Sterically Hindered Ethers","authors":"Dr. Yaseen A. Almehmadi, Anna J. Passmore, Dr. Pablo Gabriel, Prof. Dr. Darren J. Dixon","doi":"10.1002/ange.202508301","DOIUrl":"https://doi.org/10.1002/ange.202508301","url":null,"abstract":"The synthesis of sterically hindered α-tertiary and β-quaternary (neopentylic) ethers has long been constrained by the limitations of traditional SN2 and related SN1 approaches, namely low or inexistent reactivity arising from severe steric hindrance or competitive elimination/rearrangement pathways diverting the reaction outcome. Herein, we describe a general solution to the synthesis of sterically hindered ethers via an iridium-catalyzed reductive deoxygenation reaction of readily available ester and lactone starting materials. Employing commercially available, bench-stable IrCl(CO)(P[OCH(CF3)2]3)2 as a precatalyst at 1 mol% loading with 4 equivalents of tetramethyldisiloxane (TMDS) as the terminal reductant at room temperature, this practical synthetic approach to hindered ethers features a simple, mix-and-stir, single-vessel protocol under ambient conditions and produces a diverse range of both acyclic and cyclic ether products in good to excellent yields. Control experiments demonstrated that the IrCl(CO)(P[OCH(CF3)2]3)2/TMDS catalytic system could not only rapidly hydrosilylate esters to mixed silyl/alkyl hemiacetal intermediates but also catalyze the reduction of acetals directly to ethers, revealing the Lewis acidic and hydridic properties required for this deoxygenative transformation.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 40","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202508301","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145172033","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0