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Uranyl-Enabled Photocatalytic C(sp3)-H Functionalization with Azoles. 氮化铀酰光催化C(sp3)-H功能化。
IF 5.2 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-01-30 DOI: 10.1021/acs.orglett.5c05026
Yin-Ying Luo,Shu-Yun Zhang,Yan-Xin Jiang,Song-Bai Tang,Jia-Hao Ruan,Jing Su
Under mild conditions, uranyl nitrate catalyzed C(sp3)-center/azole coupling without external additives, offering a broad substrate scope and high yields (up to 95%). The method was further validated under sunlight and in scale-up experiments, highlighting its industrial potential. Experimental and theoretical studies show that uranyl nitrate acts via both hydrogen-atom transfer (HAT) and non-HAT concerted proton-electron transfer mechanisms. This approach provides a green, efficient protocol for C(sp3)-azole bond formation.
在温和的条件下,硝酸铀酰催化了C(sp3)-中心/唑偶联,无需外源添加剂,底物范围广,产率高(可达95%)。该方法在阳光下和规模实验中得到进一步验证,凸显了其工业潜力。实验和理论研究表明,硝酸铀酰具有氢原子转移和非氢原子转移两种协同质子-电子转移机制。这种方法为C(sp3)-唑键的形成提供了一种绿色、高效的方法。
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引用次数: 0
Divergent Reactivity of Diketopyrrolopyrroles: Ring-Opening with Amines. 双酮吡咯的发散反应性:与胺开环。
IF 5.2 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-01-30 DOI: 10.1021/acs.orglett.5c04654
Vitor A S Almodovar,Gonçalo F Oliveira,Nuno R Candeias,Filipe A Almeida Paz,Augusto C Tomé
We report an unprecedented reaction of a diketopyrrolopyrrole (DPP) with primary and secondary amines that results in the ring-opening of the core with loss of its fluorescence. The various characterization techniques used in this study, such as X-ray diffraction, NMR spectroscopy, mass spectrometry, and UV-vis analysis, warrant accurate identification of the structures of the newly synthesized compounds. DFT studies were also performed in order to understand the mechanism associated with this reaction.
我们报道了一个前所未有的反应二酮吡咯(DPP)与伯胺和仲胺,导致环开的核心损失其荧光。本研究中使用的各种表征技术,如x射线衍射、核磁共振光谱、质谱和紫外可见分析,保证了新合成化合物结构的准确鉴定。为了了解与该反应相关的机理,也进行了DFT研究。
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引用次数: 0
Synergistic Photoenzymatic Catalysis Enables Enantioselective Synthesis of γ-Amides via a Ternary Electron Donor-Acceptor Complex. 协同光酶催化通过三元电子供体-受体配合物实现γ-酰胺的对映选择性合成。
IF 5.2 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-01-30 DOI: 10.1021/acs.orglett.6c00199
Yao Yao,Ming-Liang Shi,Xin-Yue Fan,Ke Xu,Kun Li,Xiao-Qi Yu,Shan-Yong Chen,Na Wang
The development of photoenzymatic non-natural reactions facilitates the synthesis of challenging high-value-added chiral compounds. However, this approach typically requires enzyme engineering to enhance both the catalytic activity and selectivity. Herein, we report a synergistic photoenymatic system comprising wild-type GluER and exogenous Ru(bpy)3Cl2·6H2O that enables the photoenzymatic enantioselective hydroalkylation of olefins. In this system, Ru(bpy)3Cl2·6H2O replaces protein engineering, driving an efficient catalytic cycle. The radical initiation was by electron transfer between excited Ru(bpy)3Cl2·6H2O and an in situ-formed ternary electron donor-acceptor (EDA) complex. This synergistic photo/biocatalytic system decreases the time-consuming and labor-intensive nature while providing an environmentally friendly methodology for chemical synthesis.
光酶非自然反应的发展促进了具有挑战性的高附加值手性化合物的合成。然而,这种方法通常需要酶工程来提高催化活性和选择性。在这里,我们报道了一个由野生型GluER和外源Ru(bpy)3Cl2·6H2O组成的协同光酶系统,该系统能够实现烯烃的光酶对映选择性氢烷基化。在该体系中,Ru(bpy)3Cl2·6H2O取代了蛋白质工程,驱动了一个高效的催化循环。自由基的起始是由Ru(bpy)3Cl2·6H2O与原位形成的三元电子给受体(EDA)配合物之间的电子转移引起的。这种协同光/生物催化系统减少了耗时和劳动密集型的性质,同时为化学合成提供了一种环保的方法。
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引用次数: 0
[60]Fullerene-Fused ζ-Lactones: Synthesis and Further Transformations. 富勒烯-融合ζ-内酯的合成及进一步转化
IF 5.2 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-01-29 DOI: 10.1021/acs.orglett.5c05427
Xinmin Huang,Xu Han,Chuang Niu,Wen-Jie Qiu,Zhiwei Xu,Hai-Bin Zhou,Zheng-Chun Yin,Guan-Wu Wang
Novel and challenging [60]fullerene (C60)-fused ζ-lactones, containing an eight-membered ring, have been successfully synthesized via palladium-catalyzed annulations of C60 with 2-arylbenzoic acids. This approach employs a carboxyl-directed C-H activation strategy to facilitate lactone formation. The formed ζ-lactones undergo an unprecedented deoxygenative skeletal rearrangement in the presence of triflic anhydride to generate C60-fluorenone conjugates. The assigned structures were confirmed by single-crystal X-ray diffraction. The C60-fused ζ-lactones can be further electrochemically transformed into 1,2-hydrofullerenes. In addition, a representative ζ-lactone was efficiently employed as the third component in organic solar cells, resulting in an improvement in device performance.
通过钯催化C60与2-芳基苯甲酸环化,成功合成了一种新颖且具有挑战性的含八元环的[60]富勒烯(C60)-融合β -内酯。这种方法采用羧基导向的C-H激活策略来促进内酯的形成。形成的ζ-内酯在三酸酐的存在下经历前所未有的脱氧骨架重排,生成c60 -芴酮缀合物。通过单晶x射线衍射证实了所分配的结构。c60融合的ζ-内酯可以进一步电化学转化为1,2-氢富勒烯。此外,一种代表性的ζ-内酯被有效地用作有机太阳能电池的第三组分,从而提高了器件的性能。
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引用次数: 0
Experimental Support for a Chiral Pentacoordinate, Axially Symmetric Cationic Mn(V)-Oxo Complex as the Key Reactant in the Highly Enantioselective Catalytic Epoxidation of Olefins. 手性五配位、轴对称阳离子Mn(V)-氧配合物在烯烃高对映选择性催化环氧化反应中的实验支持。
IF 5.2 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-01-29 DOI: 10.1021/acs.orglett.5c05153
G Sudhakar Reddy,E J Corey
Reported herein are new results on the mechanism of action and scope of a recently discovered process for enantio- and position-selective epoxidation of C═C using a novel chiral Mn(II) catalyst at 3 mol %. A novel axially symmetric cationic Mn(V)-oxo complex has been found to deliver oxygen to a double bond with a strong and predictable enantiofacial preference. The method has been demonstrated for a variety of mono- and trisubstituted olefins. The rate-limiting step is not formation of the Mn(V)-oxo intermediate but transfer of oxygen from it to the olefin operating under the Curtin-Hammett principle.
本文报道了一种新的手性Mn(II)催化剂在3mol %浓度下催化C = C对构象和位置选择性环氧化反应的作用机制和作用范围的新结果。一种新型的轴对称阳离子Mn(V)-氧配合物被发现可以将氧传递到双键上,具有强的和可预测的对映面偏好。该方法已用于多种单取代烯烃和三取代烯烃。限速步骤不是Mn(V)-o中间体的形成,而是根据Curtin-Hammett原理将氧从中间体转移到烯烃中。
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引用次数: 0
Metabolic Competition between Non-reducing Polyketide Synthases Drives Hidden Chemodiversity in Deep-Sea Fungus Talaromyces radicus. 非还原性聚酮合酶之间的代谢竞争驱动深海真菌根Talaromyces
IF 5.2 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-01-29 DOI: 10.1021/acs.orglett.5c05307
Jun Wu,Wei-Chen Chen,Bowei Wen,Jing Chen,Zhuoyue Yang,Ke Lu,Zhaoxin Yao,Zhicheng Guo,Hui Qiu,Zixin Deng,Ning Li,You-Sheng Cai,Kui Hong
Genome mining of Talaromyces radicus WHUF04045 identified two unusual nrPKSs (Tr4942 and Tr2381) with distinct release mechanisms, whose precursor competition was revealed by multiomics, gene deletion, and heterologous expression. Deletion of Tr4942 activated nine new chromone derivatives (1-9) and four new naphthoquinone derivatives (11-14), which displayed significant pro-angiogenic and anti-inflammatory activities, with compound 8 showing significant anti-inflammatory effects via modulation of the NF-κB signaling pathway.
对Talaromyces radicus WHUF04045的基因组挖掘发现了两个不同寻常的nrpks (Tr4942和Tr2381),它们具有不同的释放机制,通过多组学、基因缺失和异源表达揭示了它们的前体竞争。Tr4942的缺失激活了9个新的色素衍生物(1-9)和4个新的萘醌衍生物(11-14),它们具有显著的促血管生成和抗炎活性,其中化合物8通过调节NF-κB信号通路具有显著的抗炎作用。
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引用次数: 0
Ring-Strain-Driven Annulation of Cyclopropenones with Hydrazones via Nucleophilic Phosphine Catalysis. 亲核膦催化环丙烯与腙环化反应的环状应变驱动。
IF 5.2 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-01-29 DOI: 10.1021/acs.orglett.5c05338
Shan Jiang,Xiaoqi Yang,Xiao-Le Han,Yi Wei,Xiao-Qiang Hu
Herein, we demonstrate a ring-strain-driven annulation of cyclopropenones with hydrazones via simple phosphine catalysis, providing an efficient route to structurally diverse 1,3,4-oxadiazolines and spiro-1,3,4-oxadiazolines under mild conditions. The reaction proceeds through the formation of a reactive α-ketenyl phosphorus ylide intermediate, generated by the interaction of cyclopropenone with a nucleophilic phosphine catalyst. Notably, an intriguing acyl group migration-mediated [3+2] annulation is observed with hydrazones derived from linear ketones, while a ring-opening addition/cyclization cascade takes place with cyclic hydrazones.
在此,我们通过简单的膦催化,证明了环丙烯与腙的环状驱动环,为在温和条件下制备结构多样的1,3,4-恶二唑啉和螺-1,3,4-恶二唑啉提供了有效途径。该反应是通过环丙烯与亲核膦催化剂相互作用生成反应性α-烯基磷酸基中间体来进行的。值得注意的是,线性酮衍生的腙发生了酰基迁移介导的[3+2]环化,而环状腙发生了开环加成/环化级联。
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引用次数: 0
Asymmetric Cycloaddition of 1,6-Diynes with Alkenes Enabled by Ligand-to-Metal Chirality Transfer in Cobalt/Photoredox Cooperative Catalysis. 钴/光氧化还原协同催化中配体-金属手性转移实现1,6-二炔与烯烃的不对称环加成。
IF 5.2 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-01-29 DOI: 10.1021/acs.orglett.5c05365
Takeshi Yasui,Keiji Yamada,Yuki Ishikawa,Kotoko Nakagawa,Rinto Fujii,Yoshihiko Yamamoto
Here we report a highly enantioselective cycloaddition of 1,6-diynes and alkenes mediated by cobalt/photoredox cooperative catalysis. This transformation requires a chiral monodentate phosphine ligand, which is rarely applied in such reactions because of its limited stereocontrol. DFT studies reveal that the ligand controls metal-centered chirality, enabling the synthesis of multisubstituted cyclohexadienes with excellent enantioselectivity.
在这里,我们报道了由钴/光氧化还原协同催化介导的1,6-二炔和烯烃的高度对映选择性环加成。这种转化需要手性单齿膦配体,但由于其立体控制能力有限,很少应用于此类反应。DFT研究表明,该配体控制金属中心手性,可合成具有优异对映选择性的多取代环己二烯。
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引用次数: 0
Thermal Dearomative Rearrangement of α-(Prop-2-enyl)-α'-(pyridin-2-yl) Malonate Derivatives toward 4H-Dihydroquinolizines. α-(2-丙烯基)-α'-(2-吡啶基)丙二酸酯衍生物对4h -二氢喹啉的热脱芳重排。
IF 5 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-01-29 DOI: 10.1021/acs.orglett.5c05239
Pierre Locquet, Noam Boussalem, Delphine Hatey, Fabienne Grellepois, Eric Hénon, Emmanuel Riguet, Aurélien Blanc

Reported herein is a thermally induced dearomative rearrangement of α-(aza-heteroaryl)-α'-prop-2-enyl malonate derivatives, affording 4H-dihydroquinolizine derivatives (21 examples, 26-89%). The rearrangement, assisted by microwave heating, afforded diastereoselective quinolizidine scaffolds, known for their broad biological activities. Experimental results and DFT calculations converge to support a stepwise mechanism initiated by intramolecular [1,4]-addition of pyridine nitrogen to the activated acrylate moiety followed by selective ester transfer.

本文报道了α-(杂氮杂芳基)-α'-丙-2-烯基丙二酸酯衍生物的热诱导脱芳重排,得到了4h -二氢喹啉衍生物(21例,26-89%)。这种重排,在微波加热的辅助下,提供了非对映选择性的喹诺齐啶支架,以其广泛的生物活性而闻名。实验结果和DFT计算一致支持由分子内[1,4]-吡啶氮加成到活化的丙烯酸酯部分,然后选择性酯转移引发的逐步机制。
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引用次数: 0
Copper/Photoredox Dual Catalysis for the Redox-Neutral C(sp3)-CF2H Cross-Coupling between Benzylic Bromides and Tetracoordinated Difluoromethylborates. 铜/光氧化还原双催化氧化还原中性C(sp3)-CF2H在苯溴化物和四配位二氟甲基硼酸盐之间的交叉偶联。
IF 5.2 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-01-29 DOI: 10.1021/acs.orglett.6c00060
Xiangxue Cao,Ge Lan,Zhenyu Wang,Shuai Liu,Yu Wei,Liang Xu,Huanhuan Song
A copper/photoredox dual-catalytic strategy has been developed for radical-radical C(sp3)-CF2H cross-coupling between alkyl bromides and readily accessible tetracoordinated difluoromethylborates. In this protocol, visible-light-induced single-electron oxidation of the borates generates difluoromethyl radicals (•CF2H), which are subsequently intercepted by a copper catalyst to forge C(sp3)-CF2H bonds. This redox-neutral approach proceeds without the need for stoichiometric halogen atom transfer (XAT) reagents, oxidants, or reductants, exhibits broad functional group tolerance, and enables late-stage installation of the pharmaceutically privileged CF2H motif into aliphatic frameworks.
研究了一种铜/光氧化还原双催化策略,用于烷基溴和易接近的四配位二氟甲基硼酸盐之间的自由基-自由基C(sp3)-CF2H交叉偶联。在这个方案中,可见光诱导的硼酸盐的单电子氧化产生二氟甲基自由基(•CF2H),随后被铜催化剂拦截,形成C(sp3)-CF2H键。这种氧化还原-中性方法无需化学计量卤素原子转移(XAT)试剂、氧化剂或还原剂,具有广泛的官能团耐受性,并且能够在后期将具有药学优势的CF2H基序安装到脂肪族框架中。
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引用次数: 0
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Organic Letters
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