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Ligand-Promoted Palladium-Catalyzed [4 + 4] Cycloaddition Affording Benzo[d]isothiazole 1,1-Dioxide-Fused Chiral Eight-Membered N-Heterocycles. 配体促进钯催化[4 + 4]环加成提供苯并[d]异噻唑1,1-二氧化物-熔融手性八元n -杂环。
IF 5.2 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-12-10 DOI: 10.1021/acs.orglett.5c04576
Weixin Xiao,Zhengyi Yi,Yong Liu,Lunyu Ou,Hongyun Li,Yue Zhang,Haijun Yang,Hua Fu
Synthesis of chiral eight-membered rings with high regioselectivity and stereoselectivity has been a great challenge in asymmetric catalysis. There is no report on the synthesis of benzo[d]isothiazole 1,1-dioxide-fused chiral eight-membered N-heterocycles thus far. Herein, we report a palladium-catalyzed asymmetric [4 + 4] cycloaddition of 3-styryl-1,2-benzoisothiazole 1,1-dioxides with γ-methylidene-δ-valerolactones at room temperature providing highly functionalized benzo[d]isothiazole 1,1-dioxide-fused chiral eight-membered N-heterocycles in high yields with excellent diastereoselectivity and enantioselectivity (76-89% yields, >20:1 dr, and 84-99% ee), in which the optimization of adjustable axially chiral cyclic phosphoramidite ligands developed by us is crucial for reactivity of the substrates and stereoselectivity of the products. Further modification of the synthesized products afforded other chiral eight-membered N-heterocycles containing a benzo[d]isothiazole 1,1-dioxide unit.
具有高区域选择性和立体选择性的手性八元环的合成一直是不对称催化领域的一大挑战。目前尚无合成苯并[d]异噻唑- 1,1-二氧化二苯并-熔融手性八元n杂环的报道。在此,我们报道了钯催化的不对称[4 + 4]环加成,在室温下,3-苯乙烯-1,2-苯并异噻唑- 1,1-二氧化物与γ-亚甲基-δ-戊内酯形成了高功能化的苯并[d]异噻唑- 1,1-二氧化物的手性八元n -杂环,具有优异的非对映选择性和对映选择性(产率76-89%,>20:1 dr和84-99% ee)。其中,我们开发的可调节轴手性环磷酸酰胺配体的优化对底物的反应活性和产物的立体选择性至关重要。对合成产物进行进一步修饰,得到含有苯并[d]异噻唑1,1-二氧化基的其他手性八元n -杂环。
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引用次数: 0
Synthesis of Carborane-Functionalized Macrocycles: Bond-Angle-Modulated Cavities and Cation-Mediated Assembly. 碳硼烷功能化大环的合成:键角调制腔和阳离子介导组装。
IF 5.2 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-12-09 DOI: 10.1021/acs.orglett.5c04579
Ying-Zheng Ren,Nian Si,Peng-Fei Liu,Hao-Hui Xie,Wen-Chao Zhang,Peng-Fei Cui
Herein, a novel synthetic strategy for macrocycles based on a three-dimensional carborane skeleton via a cyclization reaction was developed. Further substrate scope experiments confirm that this strategy possesses excellent reaction compatibility. In addition, the cavity size of the macrocycle can be regulated by the bonding angle, in which the size of the macrocycle cavity formed by para-carborane (180°) is larger than that formed by meta-carborane (120°). More importantly, when a pyridine group is introduced into this type of macrocycle, nanotubes can be constructed through the coordination modes of [N···Ag+···N] and [N···I+···N]. The host-guest properties of the macrocycles are also explored to show the specific encapsulation of dichloromethane molecules through van der Waals forces. This work significantly enriches the structural diversity of supramolecular macrocycles and develops unique host-guest properties of the carborane-based macrocycles.
本文提出了一种基于三维碳硼烷骨架的环化合成策略。进一步的底物范围实验证实了该策略具有良好的反应相容性。此外,大环的空腔尺寸可以通过键合角度来调节,其中对碳硼烷(180°)形成的大环空腔尺寸大于间碳硼烷(120°)形成的大环空腔尺寸。更重要的是,在这类大环中引入吡啶基团后,可以通过[N···Ag+···N]和[N···I+··N]的配位模式构建纳米管。研究了大环的主客体性质,揭示了二氯甲烷分子通过范德华力的特殊包封。这项工作极大地丰富了超分子大环的结构多样性,并开发了碳烷基大环独特的主客体性质。
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引用次数: 0
Photoinduced Ligand-to-Metal Charge Transfer Enables Iron-Catalyzed Site-Selective Oxime Ether Construction at C(sp3)-H Bonds of Silanes. 光诱导配体到金属的电荷转移使铁催化的硅烷C(sp3)-H键上的选择性肟醚结构成为可能。
IF 5.2 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-12-09 DOI: 10.1021/acs.orglett.5c04227
Zhijun Hao,Xiushan Liu,Yunfei Cai,Huifeng Yue
Herein, we present a novel iron-catalyzed regioselective C-H functionalization of silanes for the construction of oxime ethers enabled by photoinduced ligand-to-metal charge transfer (LMCT). This transformation proceeds under mild conditions using an inexpensive and commercially available iron catalyst, without the need for costly photocatalysts. The protocol features excellent site selectivity, broad substrate scope, high efficiency, and good scalability, offering a practical and economical route to organosilicon-based oxime ethers.
在这里,我们提出了一种新的铁催化硅烷的区域选择性C-H功能化,通过光诱导配体到金属电荷转移(LMCT)来构建肟醚。这种转化在温和的条件下进行,使用一种廉价的、市售的铁催化剂,而不需要昂贵的光催化剂。该方案具有良好的位点选择性、广泛的底物范围、高效率和良好的可扩展性,为有机硅基肟醚的制备提供了一条实用而经济的途径。
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引用次数: 0
B(C6F5)3-Catalyzed Dearomative [2π+2σ] Cycloaddition of 1-Naphthols with Bicyclo[1.1.0]butanes. B(C6F5)3催化1-萘酚与双环[1.1.0]丁烷的[2π+2σ]环加成反应。
IF 5.2 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-12-09 DOI: 10.1021/acs.orglett.5c04557
Lin Li,Lei Xiao,Zhongyu Yi,Yufen Zhao,Douglas W Stephan,Jing Guo
Converting planar arenes into C(sp3)-rich three-dimensional frameworks is an effective route to access bioisosteres of functional compounds. However, it remains challenging due to the inherent thermodynamic stability and kinetic inertness of planar arenes. In this work, we describe a simple, highly efficient, variable, and scalable method for the dearomative [2π+2σ] cycloaddition of 1-naphthols with bicyclo[1.1.0]butanes. Using this approach, 26 benzocyclohexanone-fused bicyclo[2.1.1]hexanes were obtained under mild reaction conditions in up to 99% yield with up to 19:1 dr.
将平面芳烃转化为富含C(sp3)的三维骨架是获取功能化合物生物同位异构体的有效途径。然而,由于平面芳烃固有的热力学稳定性和动力学惰性,它仍然具有挑战性。在这项工作中,我们描述了一种简单,高效,可变和可扩展的方法,用于1-萘酚与双环[1.1.0]丁烷的脱芳香[2π+2σ]环加成。采用该方法,在温和的反应条件下,以高达99%的收率和高达19:1的dr合成了26个苯并环己酮融合的双环己烷[2.1.1]。
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引用次数: 0
Accessing Dihydroazepines and Cyclopentanes from Enynyl Ketones. 从炔基酮提取二氢氮卓类和环戊烷。
IF 5.2 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-12-09 DOI: 10.1021/acs.orglett.5c04290
Li Li,Shiqing Huang,Yingjian Gong,Jingpeng Han,Jianwei Liu,Guangshen Wang,Baosheng Li
The stereocontrolled construction of polycyclic architectures from linear precursors remains a significant challenge, particularly for medium-sized rings, where strain and conformational flexibility hinder efficient cyclization. Herein, we report a tandem cyclization strategy converting linear precursors to polysubstituted dihydroazepines. The resulting compounds undergo acid-promoted ring contraction to cyclopentanes with five contiguous stereocenters. Overall, this strategy provides a streamlined route to architecturally sterically congested azepine- and cyclopentane-fused dihydrofuran products with a broad substrate scope and functional group tolerance.
用线性前体立体控制构造多环结构仍然是一个重大挑战,特别是对于中等大小的环,其中应变和构象灵活性阻碍了有效的环化。在此,我们报告了串联环化策略,将线性前体转化为多取代二氢氮卓类药物。所得到的化合物经过酸促进的环收缩成具有五个连续立体中心的环戊烷。总的来说,这种策略提供了一种简化的途径,使氮卓类和环戊烷融合的二氢呋喃产品具有广泛的底物范围和官能团耐受性。
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引用次数: 0
Synthesis of (Hetero)aryl Fused 4H-Quinolizin-4-ones from N-Ts Substituted (Hetero)arylamides and Pyridotriazoles. 由N-Ts取代(杂)芳酰胺和吡喃三唑合成(杂)芳基熔融4h -喹啉-4-酮。
IF 5.2 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-12-09 DOI: 10.1021/acs.orglett.5c04190
Xin Yang,Bo Mei,Yiting Chang,Hua Tian,Heng Xu,Xiaoqiao Hong,Yi Dong
This paper describes a practical synthetic method of (hetero)aryl fused 4H-quinolizin-4-ones via (hetero)aryl sp2 C-H carbenoid functionalization of (hetero)aryl amides using pyridotriazoles with good functional group tolerance. This process demonstrates excellent site-selectivity, enabling the C-H functionalization reaction directed by an amide group by overcoming the interference of strong coordination between N-heterocycles and metal catalysis. The synthetic method represents an efficient strategy with attractive application prospects, including late-stage modification of drug molecules, total synthesis of natural products, and live-cell imaging.
本文介绍了一种实用的合成方法,利用具有良好官能团耐受性的吡喃三唑,通过杂芳基sp2 C-H类羰基功能化(杂芳基)酰胺,合成(杂芳基)熔接4h -喹啉-4-酮。该工艺具有良好的位点选择性,克服了n -杂环之间强配位和金属催化的干扰,实现了酰胺基引导的C-H功能化反应。该合成方法在药物分子的后期修饰、天然产物的全合成和活细胞成像等方面具有良好的应用前景。
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引用次数: 0
Cethrene’s Catch-22: Is Trading Magnetism for Bistability Inevitable? 乙烯的第22条军规:用磁性交换双稳是否不可避免?
IF 5.2 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-12-09 DOI: 10.1021/acs.orglett.5c04279
Pauline Pfister, Daniel Čavlović, Tamara Trajkovic, Olivier Blacque, Michal Juríček
Cethrenes represent a promising platform for realizing all-organic magnetic photoswitches─provided that three requirements are met. The open form needs a thermally accessible triplet state to unlock magnetic properties, its energy relative to the closed form should lie within an accessible range, and the energy barrier between the two forms must be sufficiently high to achieve bistability. However, fulfilling the first and second criteria appear to compromise the third. Can this Catch-22 be solved? [Oxford English Dictionary defines a Catch-22 as a difficult situation or problem which cannot be resolved because the conditions necessary for its resolution are paradoxical or conflicting, with allusion to Joseph Heller’s 1961 novel of the same name.]
只要满足三个要求,就可以使用乙醚来实现全有机磁性光开关。开放形式需要一个热可接近的三重态来解锁磁性,其相对于封闭形式的能量应该在一个可接近的范围内,并且两种形式之间的能量势垒必须足够高以实现双稳定。然而,满足第一个和第二个标准似乎会损害第三个标准。这个第22条军规能解决吗?[《牛津英语词典》对Catch-22的定义是:由于解决问题的必要条件是矛盾的或相互冲突的,所以无法解决的困境或问题,这是约瑟夫·海勒1961年的同名小说的典故。]
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引用次数: 0
A Cyclic tris-BODIPY Complex Derived from Dithienopyrrole Embedded [48]Dodecaphyrin (1.0.0.1.0.0.1.0.0) as Photoacoustic Contrast Agent 由二噻吩吡咯衍生的环状三体吡啶配合物嵌入[48]十二葡萄蛋白(1.0.0.1.0.0.1.0.0)作为光声造影剂
IF 5.2 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-12-09 DOI: 10.1021/acs.orglett.5c04304
Gayathri Krishnan, Jayaprakash Ajay, Aathira Edwin, Thondikkal Sulfikarali, Deepayan Samanta, M. Suheshkumar Singh, Sabapathi Gokulnath
A rigid dithienopyrrole embedded dodecaphyrin and its tris-BODIPY (bis(triisopropylsilyl-ethynyl)-substituted boron-dipyrromethene (BODIPY)) complex have been synthesized. DFT analysis showed a “ruffled” structure for dodecaphyrin and a saddle-shaped structure for tris-BODIPY. Increased conjugation of tris-BODIPY 2 showed a red-shifted absorption band (ca. 115 nm) with strong absorption in the NIR-I region as compared to its freebase analogue 1. These optical features along with nonfluorescent characteristics of 2 displayed an efficient photoacoustic imaging contrast agent.
合成了一种刚性二噻吩吡咯包埋的十二葡萄蛋白及其三BODIPY(双(三异丙基硅-乙基)取代硼-二吡咯甲烷(BODIPY))配合物。DFT分析显示,十二葡萄蛋白为“褶皱”结构,三体蛋白为鞍状结构。增加共轭的tris-BODIPY 2显示出一个红移的吸收带(约115 nm),在nir - 1区有较强的吸收。这些光学特征以及2的非荧光特征显示了它是一种有效的光声成像造影剂。
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引用次数: 0
Newcomer to the Calixarene Family: Synthesis and Characterization of Selenacalix[4]arene. 杯芳烃家族的新成员:硒杯芳烃的合成与表征。
IF 5.2 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-12-09 DOI: 10.1021/acs.orglett.5c04133
Michal Churý,Tadeáš Petrů,Radek Staník,Jan Sýkora,Václav Eigner,Pavel Lhoták
In this work, we describe a general and efficient fragment condensation method for the synthesis of monoselenacalix[4]arene as a new member of the broad calixarene family. The key fragments were obtained from the starting p-tert-butylphenol by reaction with in situ generated SeCl2 or from its formyl derivative by reaction with SeO2 in pyridine. The availability of both fragments allowed us to test two different independent macrocyclization routes, leading to the final selenacalixarene in good yields. The first successful attempts to immobilize the new system were made, and the basic dynamics of the macrocycles in solution were studied using VT NMR techniques. The selenium analogue of calix[4]arene was successfully immobilized in the cone conformation, suggesting its potential use in supramolecular chemistry.
本文介绍了一种通用、高效的单硒杯芳烃[4]片段缩合合成方法。关键片段由起始对叔丁基苯酚与原位生成的SeCl2反应得到,或由其甲酰基衍生物与吡啶中的SeO2反应得到。这两种片段的可用性使我们能够测试两种不同的独立大环化路线,从而获得高产的最终硒化杯芳烃。首次成功地固定了新体系,并利用VT核磁共振技术研究了溶液中大环的基本动力学。杯状芳烃的硒类似物成功地固定在锥形构象中,表明其在超分子化学中的潜在应用。
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引用次数: 0
Photoinduced Lanthanum Catalysis: C-H Activation and Spirocyclization. 光诱导镧催化:C-H活化和螺旋环化。
IF 5.2 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-12-09 DOI: 10.1021/acs.orglett.5c04699
Zhenhong Gan,Xiaoyan Cai,Liming Chen,Lele Zhang,Jiaxin Lin,Mingqiang Huang,Lina Cai,Shunyou Cai
Lanthanum-catalyzed tandem C(sp3)-H oxidation/spirocyclization under ambient conditions using molecular oxygen is reported. This method exhibits broad functional group tolerance and enables precise functionalization of complex scaffolds. The reaction proceeds via a light-absorbing lanthanum complex assembled through in situ multicomponent coordination, operating through synergistic intramolecular energy transfer and single-electron transfer pathways. This approach provides efficient access to diverse N,O- and O,O-spirocyclic compounds. Mechanistic studies establish that lanthanum bromide acts not only as the photosensitizer metal center, generating bromine radicals for C-H cleavage, but also as a Lewis acid catalyst promoting cyclization and spirocyclization.
报道了环境条件下镧催化的C(sp3)-H串联氧化/螺旋环化反应。该方法具有广泛的官能团耐受性,能够精确地实现复杂支架的功能化。反应通过吸收光的镧配合物进行,该配合物通过原位多组分配位组装,通过协同的分子内能量转移和单电子转移途径进行。这种方法提供了多种N,O-和O,O-螺旋环化合物的有效途径。机理研究表明,溴化镧不仅可以作为光敏剂金属中心,生成溴自由基进行C-H裂解,还可以作为Lewis酸催化剂促进环化和螺旋环化。
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引用次数: 0
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Organic Letters
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