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Palladium/copper bimetallic system-catalyzed cascade cyclization of N-allyl Ynamides and o-haloanilines: access to multifunctional benzimidazoles 钯/铜双金属系统催化n -烯丙基酰胺和邻卤苯胺的级联环化:获得多功能苯并咪唑
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-24 DOI: 10.1039/d6qo00038j
Yi-Yun Zhang, xuheng yang, Ai-Ming Wen, Fang Wang, Jian Huang, Jianfang Wang, Cheng-an Tao
A one-pot synthesis of 1,2-disubstituted multifunctional benzimidazole derivatives starting from N-Allyl Ynamides and o-Haloanilines has been introduced. The mechanistic study suggests that the reaction proceeds via a Pd-catalyzed nucleophilic addition of N-allyl ynamides to the amino group of the o-haloanilines to form a amidine intermediate, followed by Cu-catalyzed intramolecular cyclization. The reaction could also be performed on a multi-gram scale with the same efficiency.
介绍了以n -烯丙基酰胺和邻卤代苯胺为起始原料一锅合成1,2-二取代多功能苯并咪唑衍生物的方法。机理研究表明,该反应是通过pd催化的n -烯丙基酰胺的亲核加成到邻卤苯胺的氨基上形成酰胺中间体,然后是cu催化的分子内环化。该反应也可以在多克尺度上以相同的效率进行。
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引用次数: 0
Group 14 heavier 1,4-dimetallabenzenes: Influence of Aromaticity, Open-Shell Character and Strain on Small Molecule Activation 14族较重的1,4-二金属苯:芳香性、开壳特性和菌株对小分子活化的影响
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-24 DOI: 10.1039/d6qo00006a
Daniel Gónzalez-Pinardo, Israel Fernandez
The influence of the aromaticity, diradical character and strain on the reactivity of Group 14 heavier 1,4-dimetallabenzenes (E = Si, Ge, Sn) has been investigated using quantum-chemical calculations. To this end, the activation reactions of small molecules (dihydrogen and acetylene) promoted by these species have been investigated. It is found that the lighter systems (E = Si and Ge) are significantly more reactive than their 1,4-distannabenzene analogue, despite the latter exhibiting a larger diradical character. According to the Activation Strain Model of reactivity, the reduced reactivity of the heaviest species is directly related to its highly bent, chair-like equilibrium geometry, which must undergo substantial deformation (in comparison with its lighter congeners) to reach the corresponding transition state geometry.
用量子化学方法研究了14族重1,4-二金属苯(E = Si, Ge, Sn)的芳构性、双自由基性质和应变对其反应性的影响。为此,研究了这些物质促进的小分子(二氢和乙炔)的活化反应。结果发现,较轻的体系(E = Si和Ge)比它们的1,4-二苯基类似物反应性更强,尽管后者表现出更大的双自由基特征。根据反应性的激活应变模型,最重物质的反应性降低与其高度弯曲的椅子状平衡几何直接相关,与较轻的同类相比,它必须经历大量变形才能达到相应的过渡态几何。
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引用次数: 0
Theoretical investigation on the mechanism of Ni0(acetylide carbanion)-ate complex-catalyzed C(sp2)–F bond activation and the origin of the counterion effect on reactivity Ni0(乙酰基碳离子)-酸配合物催化C(sp2) -F键活化机理的理论研究及对反应性的反作用力的来源
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-23 DOI: 10.1039/d5qo01757b
Xiao-Xia You, Ling-Qi Meng, Xu Liu, Li-Li Wang, Xin-Cheng Xu, Rong-Lin Zhong, Zhong-Min Su
This study employs density functional theory (DFT) calculations to elucidate the mechanism and alkali metal-dependent reactivity in the Ni0-catalyzed C(sp2)–F bond activation of fluoronaphthalenes, assisted by lithium acetylides. The results reveal that the energy barrier for C(sp2)–F bond activation initiated by the acetylide carbanion is 30.1 kcal mol−1, significantly higher than that (18.5 kcal mol−1) for the ethide carbanion-initiated one, due to the notably weaker nucleophilicity of the acetylide carbanion. Interestingly, the reaction between lithium acetylides and the pre-catalyst Ni0(cod)2 generates a Ni0(acetylide carbanion)-ate complex, in which high nucleophilicity is localized at the Ni0-center. Significantly, the energy barrier for C(sp2)–F bond activation catalyzed by the Ni0(acetylide carbanion)-ate complex via an inner-sphere nucleophilic aromatic substitution (SNAr) pathway is considerably lowered to 25.3 kcal mol−1. Theoretical analysis clarifies that the distinct reactivity of the ate complex stems from coordination of the acetylide carbanion to the Ni0 center, with strong Li⋯F interactions serving as a key driving force to stabilize the transition state. This work provides a comprehensive insight into transition metal-catalyzed C–F bond activation with the assistance of an acetylide carbanion, which is expected to offer a theoretical perspective for the rational design of C–F functionalization strategies.
本研究采用密度泛函理论(DFT)计算阐明了镍催化氟萘C(sp2) -F键活化的机理和碱金属依赖的反应性,并辅助乙酰化锂。结果表明,乙酰基碳离子激活C(sp2) -F键的能垒为30.1 kcal mol−1,明显高于乙胺碳离子激活C(sp2) -F键的能垒(18.5 kcal mol−1),这是由于乙酰基碳离子的亲核性明显较弱。有趣的是,乙酰化锂与预催化剂Ni0(cod)2之间的反应生成了Ni0(乙酰化锂碳离子)-酸配合物,其高亲核性定位于Ni0中心。值得注意的是,Ni0(乙酰碳离子)-酸配合物通过球内亲核芳香取代(SNAr)途径催化的C(sp2) -F键激活的能垒大大降低到25.3 kcal mol−1。理论分析表明,ate复合物的独特反应性源于乙酰碳离子与Ni0中心的配位,强Li⋯F相互作用是稳定过渡态的关键驱动力。本研究对过渡金属在乙基碳离子的辅助下催化C-F键活化提供了全面的见解,有望为合理设计C-F功能化策略提供理论视角。
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引用次数: 0
Pyrazolium-Ylide [3+2] Cycloaddition/Oxidative Aromatization for the Construction of 1H-pyrrolo[1,2-b]pyrazoles 吡唑-吡啶[3+2]环加成/氧化芳构化构造1h -吡咯[1,2-b]吡唑
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-21 DOI: 10.1039/d6qo00070c
Motohiro Yasui, Tatsuya Tsumori, Masato Morita, Shigeyuki Yamada, Tsutomu Konno
Despite their simple 10π aromatic nature and considerable functional potential, the chemistry of 5/5-fused N-heteroaromatic systems remains underdeveloped. Herein, we report a general strategy for accessing 1H-pyrrolo[1,2-b]pyrazoles, a largely unexplored “orphan” class of heterocycles. The methodology features the generation of pyrazolium ylides followed by [3+2] cycloaddition with alkynes under mild conditions, and a subsequent oxidative aromatization step that effectively suppresses undesired ring-opening and excessive addition pathways. The substrate scope demonstrates broad functional-group tolerance and accommodates diverse substitution patterns. Combined experimental and computational studies indicate a stepwise cycloaddition mechanism, the involvement of intrinsically unstable cycloadducts, and the presence of competing pathways that render the chemoselectivity highly sensitive to subtle changes in reaction conditions. Finally, downstream derivatization highlights the utility of the 5/5-fused framework as a versatile platform for constructing more structurally complex and/or functionally enriched molecules.
尽管具有简单的10π芳香族性质和相当大的功能潜力,但5/5-融合n -杂芳香体系的化学性质仍然不发达。在此,我们报告了一种获取1h -吡咯[1,2-b]吡唑的一般策略,这是一种基本上未被开发的“孤儿”类杂环。该方法的特点是在温和条件下与炔进行[3+2]环加成,然后生成吡唑酰基化合物,然后进行氧化芳构化步骤,有效抑制不希望的开环和过多的加成途径。底物范围显示出广泛的官能团耐受性和适应不同的取代模式。实验和计算相结合的研究表明,一个逐步环加成机制,内在不稳定的环加合物的参与,以及竞争途径的存在,使得化学选择性对反应条件的细微变化高度敏感。最后,下游衍生化强调了5/5融合框架作为构建结构更复杂和/或功能更丰富的分子的通用平台的实用性。
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引用次数: 0
Pd(PPh3)4-Catalyzed Regioselective C–H para-Allylation of N,N-Dialkylanilines using Vinyl Benzoxazinanones Pd(PPh3)4催化乙烯基苯并恶嗪酮对N,N-二烷基苯胺的C-H对烯丙基化反应
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-21 DOI: 10.1039/d6qo00093b
Lu Pei, Xiaolin Liu, Ding-Jun Zhang, Hui-Hong Tian, Ling-Dan Zhu, Bangguo Wei
A Pd(PPh3)4-catalyzed regioselective C–H para allylation process was developed for the reaction of N,N-dialkylanilines with vinyl benzoxazinanones. Such transformation demonstrated a novel application of vinyl benzoxazinanone reagents, allowing for the introduction of an alkenyl group exclusively to the para position of aniline derivatives. As a result, a series of N,N-dialkylaniline derivatives with para allyl type substitutions were synthesized with excellent regioselectivities (E:Z ratio >19:1).
研究了Pd(PPh3)4催化的N,N-二烷基苯胺与乙烯基苯并恶嗪酮的区域选择性C-H对烯丙基化反应。这种转化证明了乙烯基苯并恶嗪酮试剂的一种新应用,允许在苯胺衍生物的对位上专门引入烯基。结果,合成了一系列具有对烯丙基型取代的N,N-二烷基苯胺衍生物,具有优异的区域选择性(E:Z比>;19:1)。
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引用次数: 0
Advances in the Construction of Boryl Cyclobutanes 硼基环丁烷结构的研究进展
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-21 DOI: 10.1039/d6qo00008h
Kanak Kanti Das, Sutapa Dey
Boryl-substituted cyclobutanes have emerged as valuable building blocks that merge the structural rigidity and strainenabled reactivity of four-membered rings with the versatile synthetic utility of organoboron chemistry. Here, the recent advances in the synthesis of boryl-substituted cyclobutanes, a class of strained, sp³-rich building blocks that combine the structural rigidity of cyclobutanes with the exceptional versatility of organoboron chemistry, have been summarized. Emphasis is placed on strategies that exploit boronate complex reactivity and 1,2-migration processes to overcome the inherent challenges associated with four-membered ring formation. Thermal, photochemical, and transition-metalcatalysed approaches are discussed, highlighting how strain-release, radical polar crossover, and σ-bond activation enable efficient and stereocontrolled cyclobutane construction. Key mechanistic insights that govern selectivity and reactivity also have been outlined across diverse platforms.2.
硼基取代环丁烷已成为一种有价值的构建模块,它将四元环的结构刚性和应变反应性与有机硼化学的多功能合成用途结合起来。在这里,总结了最近在合成硼取代环丁烷方面的进展,这是一类应变的,富含sp³的构建块,结合了环丁烷的结构刚性和有机硼化学的特殊通用性。重点放在利用硼酸配合物反应性和1,2-迁移过程的策略上,以克服与四元环形成相关的固有挑战。讨论了热、光化学和过渡金属催化的方法,强调了应变释放、自由基极性交叉和σ键活化如何使环丁烷结构高效和立体控制。在不同的平台上,还概述了控制选择性和反应性的关键机制见解。
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引用次数: 0
A Modular Approach toward 5,6,7,8-functionalized Acepleiadylene derivatives 5,6,7,8功能化乙酰二甲苯衍生物的模块化研究
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-20 DOI: 10.1039/d5qo01765c
Shengchen Wei, Yingjie Peng, Dan Shi, Xiang-Zhao Zhu, Songhua Chen, Lili Xie, Yuanming Li
This work presents the first modular synthesis method for Acepleiadylene derivatives which were synthesized through Suzuki coupling of biphenyl compounds with acenaphthenylboronic acid 1 followed by 2,3-dichloro-5,6-dicyano-1,4benzoquinone (DDQ) oxidation. Through the control of functional blocks, the manipulation of the structure of Acepleiadylene derivatives was achieved, which in turn different photoelectric properties. Modification and π-extension of APD were accomplished at the 5, 6, 7, and 8 positions. A comprehensive investigation of their structural, photophysical, and electronic properties was studied by experiment and theoretical calculations.
本文首次采用模块化合成方法,将联苯化合物与苊基硼酸1铃木偶联,然后用2,3-二氯-5,6-二氰-1,4苯醌(DDQ)氧化法合成了对二甲苯衍生物。通过对功能块的控制,实现了对乙炔衍生物结构的操纵,从而改变了其光电性能。APD在5、6、7、8位进行了修饰和π扩展。通过实验和理论计算对它们的结构、光物理和电子性质进行了全面的研究。
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引用次数: 0
Phosphorothiosulfonates: New Radical Phosphorothiolation Reagents for Photocatalytic Cyclization of Alkenes/Alkynes 磷硫代磺酸盐:用于光催化烯烃/炔环化的新型自由基磷硫代试剂
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-20 DOI: 10.1039/d6qo00063k
Xiang Liu, Mingyang Chen, Peng Liao, Yitai Fu, Qian Wang, Yanlong Ma, Hua Cao
The direct radical phosphorothiolation of alkenes/alkynes has been severely limited by the lack of practical and efficient radical phosphorothiolation reagents. Herein, we report the first synthesis of phosphorothiosulfonates as competent radical –S-P(O)(OR)₂ precursors. Under mild photoredox conditions, these reagents enable metal-free and oxidant-free phosphorothiolation/cyclization of diverse alkenes and alkynes, affording a broad range of phosphorothiolated N-heterocycles and carbocycles in good yields. This strategy offers a straightforward and general platform for the rapid installation of –S-P(O)(OR)₂ groups, significantly expanding the chemical space for radical phosphorothiolation chemistry.
由于缺乏实用、高效的自由基硫代化试剂,烯烃/炔的直接自由基硫代化受到了严重的限制。在此,我们首次合成了磷硫代磺酸盐作为活性自由基-S-P (O)(OR) 2前体。在温和的光氧化还原条件下,这些试剂可以实现各种烯烃和炔烃的无金属和无氧化剂的磷硫化/环化,以高产率提供广泛的磷硫化n杂环和碳环。该策略为快速安装-S-P (O)(OR) 2基团提供了一个简单而通用的平台,显着扩大了自由基磷酸化硫基化学的化学空间。
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引用次数: 0
Cobalt-Catalyzed C−H Annulation of Aliphatic Amides with Maleimides: Chemodivergent (4+1) and (3+2) Pathways 钴催化脂肪族酰胺与马来酰亚胺的C - H环化:化学发散(4+1)和(3+2)途径
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-19 DOI: 10.1039/d6qo00080k
Celia Sánchez, Juan Carlos Carretero, Ines Alonso, Nuria Rodriguez, Javier Adrio
Chemodivergent C−H annulation of aliphatic amides with maleimides has been achieved under cobalt-catalysis, enabling access to distinct (4+1) and (3+2) outcomes. These protocols, utilizing a readily available CoII catalyst, deliver a powerful strategy for the synthesis of a diverse range of spiro-γ-lactams (spiropyrrolidin-2-ones) and bicyclic pyrrolidin-2,5-diones. The combination of DFT and experimental studies provides mechanistic insight into both processes, revealing the origins of their diastereo- and chemoselectivity.
在钴催化下,已经实现了脂肪族酰胺与马来酰亚胺的化学发散C - H环化,从而获得不同的(4+1)和(3+2)结果。这些方案,利用现成的CoII催化剂,提供了一个强大的策略,合成各种螺-γ-内酰胺(螺吡咯烷-2-酮)和双环吡咯烷-2,5-二酮。DFT和实验研究的结合提供了对这两个过程的机制洞察,揭示了它们的非立体和化学选择性的起源。
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引用次数: 0
Organocatalytic enantioselective C–H allenylation of carbazoles with propargylic alcohols via remote 1,8-conjugate addition 邻域1,8-共轭加成法催化咔唑与丙炔醇的对映选择性丙烯化反应
IF 5.4 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-18 DOI: 10.1039/d6qo00064a
Xiaoyi Deng, Hanzhuo Huang, Jun Huang, Gong Chen, Yi Liu, Jiang Weng, Wenrun Zhu
An efficient method for the remote asymmetric C–H allenylation of carbazoles with propargylic alcohols via 1,8-conjugate addition has been developed. This strategy employs aza-para-quinone methides, generated in situ from α-(4-aminophenyl) propargylic alcohols, as versatile electrophilic intermediates. With chiral phosphoric acid catalysis, a wide range of C3-allenylated carbazole derivatives were obtained in high yields with excellent enantioselectivities (23 examples, up to 93% yield and 97% ee).
提出了一种利用1,8-共轭加成法使咔唑与丙炔醇发生远端不对称C-H烯化反应的有效方法。该策略采用了由α-(4-氨基苯基)丙炔醇原位生成的偶氮对醌方法,作为多功能亲电中间体。在手性磷酸催化下,广泛的c3 -烯丙化咔唑衍生物以高收率获得了优异的对映选择性(23个例子,高达93%的收率和97%的ee)。
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引用次数: 0
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Organic Chemistry Frontiers
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