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Base-Promoted Conversion of Propargylic Alcohols to 1,3-Enynes 丙炔醇碱促进转化为1,3-炔
IF 5.2 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-04 DOI: 10.1021/acs.orglett.6c00196
Morgane Delattre,Milena Wiegand,Qian Wang,Jieping Zhu
Under acidic conditions, propargylic alcohols undergo Meyer–Schuster or Rupe rearrangements to afford two isomeric α,β-unsaturated ketones. Herein, we disclose a mechanistically distinct base-mediated regioselective conversion of TMS ethers of propargylic alcohols to 1,3-enynes in high yields with broad functional-group compatibility. Alternatively, trapping of the in situ-generated lithium acetylide with electrophiles enables access to functionalized internal 1,3-enynes. Owing to the ready accessibility of propargylic alcohols, this method provides a practical and attractive entry to synthetically valuable 1,3-enynes.
在酸性条件下,丙炔醇经过Meyer-Schuster或Rupe重排得到两个异构体α,β-不饱和酮。在此,我们揭示了一种机制上独特的碱基介导的丙炔醇的TMS醚到1,3-炔的高收率和广泛的官能团相容性的区域选择性转化。或者,用亲电试剂捕获原位生成的乙酰化锂可以获得功能化的内部1,3-炔。由于丙炔醇的易得性,这种方法为合成有价值的1,3-炔提供了一个实用和有吸引力的入口。
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引用次数: 0
Regioselective Thiolation and Selenylation of Cyclic Diaryl λ3-Bromanes Enabled by Visible-Light Photocatalysis 可见光催化下环二芳基λ3-溴基的区域选择性硫基化和硒化
IF 5.2 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-04 DOI: 10.1021/acs.orglett.5c05455
Xue-Ying Yang,Qiang Wang,Si-Rui Jia,Shi-Yu Fu,Ming-Chuan Wang,Zhi-Yue Dong,Wan-Xuan Zhang,Bin-Jie Li,Wen-Jing Xiao
Despite the broad utility of cyclic diaryl λ3-bromanes as aryne precursors for nucleophilic additions by heteroatom-based nucleophiles under mild basic conditions, their capacity to install arylchalcogen bonds in a regioselective manner is largely unexplored and challenging. The higher oxidative addition barrier of cyclic diaryl λ3-bromanes relative to their iodine analogues leads to transition-metal-catalyzed aryl–chalcogen bond formation requiring more forcing conditions, which decreases the regioselectivity. Moreover, the oxidizing character of hypervalent bromanes might be problematic. Herein, we disclose a photocatalytic strategy to achieve highly regioselective thiolation and selenylation of cyclic diaryl λ3-bromanes. This reaction proceeds under mild reaction conditions and exhibits a broad substrate scope with a good functional group tolerance and excellent regioselectivity.
尽管环二芳基λ3-溴作为杂原子型亲核试剂在温和碱性条件下亲核加成的芳烃前体具有广泛的用途,但它们以区域选择性方式安装芳基硫键的能力在很大程度上尚未被探索和挑战。环二芳基λ3-溴相对于其碘类似物具有较高的氧化加成势,导致过渡金属催化的芳基-硫键形成需要更多的强制条件,从而降低了区域选择性。此外,高价溴的氧化特性可能存在问题。在此,我们揭示了一种光催化策略,以实现环二芳基λ3-溴的高度区域选择性硫基化和硒化。该反应在温和的反应条件下进行,表现出广泛的底物范围,具有良好的官能团耐受性和优异的区域选择性。
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引用次数: 0
Hydrocarbon-Involved Sulfoxide Deoxygenation via Bifunctional Iron-Enabled Electron Buffering and Ligand-to-Metal Charge Transfer 通过双功能铁电子缓冲和配体到金属电荷转移的烃类亚砜脱氧
IF 5.2 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-03 DOI: 10.1021/acs.orglett.6c00033
Lifang Wang, Bolin Qiao, Wenlong He, Ran Xu, Shuyang Liu, Hui Zi, Fangyi Qu, Ziyi Xu, Ruixiao Tian, Shi-Jun Li, Yu Lan, Yunhe Jin
Sulfur-containing compounds are essential motifs of natural molecules. We herein report a photoinduced iron-catalyzed strategy for efficient sulfoxide deoxygenation under mild conditions. The iron catalyst as the sole additive acts dually: it activates hydrocarbon reductants (also as a solvent) via a ligand-to-metal charge transfer pathway and serves as an “electron buffer” to regulate subsequent electron transfer. This unique mechanism enables a non-chromatography protocol with high efficiency (majority at >95%, up to 99%) and selectivity. The operationally simple method exhibits broad functional group tolerance and wide application in late-stage transformation of drug-derived sulfoxides into bioactive sulfides.
含硫化合物是天然分子的基本基元。本文报道了一种在温和条件下光诱导铁催化亚砜高效脱氧的策略。铁催化剂作为唯一的添加剂具有双重作用:它通过配体到金属的电荷转移途径激活碳氢化合物还原剂(也作为溶剂),并作为“电子缓冲器”调节随后的电子转移。这种独特的机制使非色谱协议具有高效率(大多数为95%,高达99%)和选择性。该方法操作简单,具有广泛的官能团耐受性,在药物衍生亚砜转化为生物活性硫化物的后期应用广泛。
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引用次数: 0
Cu-Catalyzed One-Pot Synthesis of Trifluoromethylated β-Lactams by Reaction of Nitrosoarenes, Trifluorodiazoethane and Arylacetylenes 铜催化一锅法合成亚硝基芳烃、三氟重氮乙烷和芳基乙炔的三氟甲基化β-内酰胺
IF 5.2 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-03 DOI: 10.1021/acs.orglett.6c00097
Usha Yadav, Sanoop P. Chandrasekharan, Anamika Dhami, Kishor Mohanan
In this paper, we disclose the utility of trifluorodiazoethane in forging trifluoromethylated β-lactams through a streamlined, one-pot Cu-catalyzed reaction involving nitrosoarenes and alkynes. This process involves the in situ generation of trifluoromethylnitrones from trifluorodiazoethane and nitrosoarenes, followed by their reaction with arylacetylenes under Kinugasa conditions, leading to the formation of trifluoromethylated β-lactams. A broad scope of reaction partners, including the Seyferth–Gilbert reagent, various nitrosoarenes, and alkynes, was demonstrated, along with an illustration of the potential of this strategy through multiple synthetic modifications.
在本文中,我们揭示了三氟重氮乙烷在三氟甲基化β-内酰胺中的应用,通过一个流线型的、一锅铜催化的反应,涉及亚硝基芳烃和炔烃。该工艺涉及由三氟重氮乙烷和亚硝基芳烃原位生成三氟甲基硝基酮,然后在Kinugasa条件下与芳基乙炔反应,形成三氟甲基化β-内酰胺。广泛的反应伙伴,包括Seyferth-Gilbert试剂,各种亚硝基芳烃和炔烃,展示了通过多种合成修饰这种策略的潜力。
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引用次数: 0
Electrochemical Activation of α-Carbonyl Alkoxyamines for Direct Nucleophilic Substitution α-羰基烷氧胺直接亲核取代的电化学活化
IF 5.2 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-03 DOI: 10.1021/acs.orglett.5c04873
John Putziger, Elya Kandahari, Song Lin
The reactivity and synthetic utility of TEMPO-derived alkoxyamines as functional handles remains insufficiently explored. This report interrogates the factors governing the stereospecific substitution of electroactivated TEMPO-derived α-carbonyl alkoxyamines. Concurrent with direct electrolysis, electroanalytical studies and theoretical calculations provided a complementary platform by which one could predict the efficacy for substrates to undergo desired substitution using benzoic acid or N-sulfonyl carbamate nucleophiles.
tempo衍生的烷氧基胺作为功能手柄的反应性和合成用途仍未得到充分的探索。本报告探讨了控制电活化tempo衍生的α-羰基烷氧胺立体特异性取代的因素。在直接电解的同时,电分析研究和理论计算提供了一个互补的平台,通过这个平台,人们可以预测底物在苯甲酸或n -磺酰基氨基甲酸酯亲核试剂的替代作用。
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引用次数: 0
Copper-Catalyzed Dearomative Cyclopropanation of Benzofurans with Diynes via Vinyl Cations 乙烯基阳离子催化苯并呋喃与炔的脱芳环丙烷化反应
IF 5.2 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-03 DOI: 10.1021/acs.orglett.5c05386
Yi-Kao Xu,Yuan-Qing Dong,Jun Jiang,Cui-Ting Li,Wei-Min He,Gongde Wu,Bo Zhou,Long-Wu Ye
Dearomative cyclopropanation of benzofurans is a powerful strategy for the assembly of valuable O-heterocycles. However, transition metal-catalyzed cyclopropanation of benzofurans is generally limited to diazo compounds. Herein, a copper-catalyzed dearomative cyclopropanation of benzofurans with diynes via vinyl cations is described, enabling the atom-economical and practical synthesis of various cyclopropa[b]benzofurans in generally moderate to excellent yields. Furthermore, preliminary studies on asymmetric catalysis reveal that the desired chiral cyclopropa[b]benzofurans could be synthesized with good to excellent ee’s.
苯并呋喃的脱芳环丙烷化是合成有价o -杂环的有效途径。然而,过渡金属催化的苯并呋喃的环丙烷化通常仅限于重氮化合物。本文描述了一种铜催化的苯并呋喃通过乙烯基阳离子与二炔进行脱芳环丙化反应,使各种环丙[b]苯并呋喃的原子经济性和实用性合成成为可能,收率一般为中等至优异。此外,不对称催化的初步研究表明,手性环丙[b]苯并呋喃可以在良好到优异的ee条件下合成。
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引用次数: 0
A Single Residue Switch Controls Isomer Selectivity in the Myxobacterial Isobonnadiene Synthase 一个单残基开关控制黏菌异黄二烯合成酶的异构体选择性
IF 5.2 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-03 DOI: 10.1021/acs.orglett.6c00100
Mohammed M. A. Ahmed, Jordan Nafie, Jeffrey D. Rudolf
Myxobacterial terpenoids are rare and only a few myxobacterial terpene synthases are known. A terpene synthase, IbdS, from Polyangium aurulentum sp. SDU3-1 was found to produce the Δ9,10 isomer (1) of the spirocyclic 6/7/5-tricyclic bonnadiene, along with several 6/10-eunicellanes and cembrenoids as minor products. Sequence comparison and site-directed mutagenesis of IbdS and the actinobacterial bonnadiene synthase revealed a single residue switch at position 57 controlling isomer selectivity.
粘菌萜类化合物是罕见的,只有少数粘菌萜类合成酶是已知的。发现来自Polyangium aurulentum sp. SDU3-1的萜烯合成酶IbdS可产生螺环6/7/5-三环苯二烯的Δ9,10异构体(1),以及几种6/10-单胞烷和小烯类化合物。对IbdS和放线菌bonnadiene合成酶的序列比较和定点诱变发现,57号位点存在一个控制异构体选择性的单残基开关。
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引用次数: 0
Redox-Active Sulfonyl Hydrazones as Programmable Sulfur Transfer for Nickel-Catalyzed C–S Coupling with Organic Halides 氧化还原活性磺酰腙作为镍催化C-S与有机卤化物偶联的可编程硫转移
IF 5.2 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-03 DOI: 10.1021/acs.orglett.5c05399
Binglian Yang,Liguang Ji,Hui Wang,Fangcan Liang,Mengfan Zheng,Ji-Quan Liu,Chao-Jun Li,Dianhu Zhu
The utilization of hydrazones as carbon or nitrogen sources in transition-metal-catalyzed synthetic chemistry has been well developed; however, their application as electrophilic sulfur cation surrogates remains uncharted territory. Herein, we report the unexpected discovery that sulfonyl hydrazones serve as programmable sulfur transfer in nickel-catalyzed C–S coupling with a broad range of organic halides. This method forges the nickel catalytic cycle toward selective C–S cross-coupling while effectively suppressing the competing formation of conventional C–C coupling products. Mechanistic studies indicate that the success of this strategy stems from the favorable reduction potential imparted by the electron-withdrawing SO2R group, which enables manganese to reduce the hydrazones in situ, generating key electrophilic sulfur species to engage in a distinctive nickel catalytic cycle that favors C–S over C–C bond formation.
在过渡金属催化合成化学中,腙作为碳源或氮源的应用已经得到了很好的发展;然而,它们作为亲电性硫阳离子替代品的应用仍然是未知的领域。在此,我们报告了意想不到的发现,磺酰腙在镍催化的C-S偶联中与广泛的有机卤化物起可编程硫转移作用。该方法使镍催化循环朝着选择性C-S交叉偶联的方向发展,同时有效抑制了传统C-C偶联产物的竞争性形成。机理研究表明,这一策略的成功源于具有吸电子功能的SO2R基团所赋予的有利还原电位,它使锰能够原位还原腙,产生关键的亲电性硫物质,参与独特的镍催化循环,有利于C-S而不是C-C键的形成。
{"title":"Redox-Active Sulfonyl Hydrazones as Programmable Sulfur Transfer for Nickel-Catalyzed C–S Coupling with Organic Halides","authors":"Binglian Yang,Liguang Ji,Hui Wang,Fangcan Liang,Mengfan Zheng,Ji-Quan Liu,Chao-Jun Li,Dianhu Zhu","doi":"10.1021/acs.orglett.5c05399","DOIUrl":"https://doi.org/10.1021/acs.orglett.5c05399","url":null,"abstract":"The utilization of hydrazones as carbon or nitrogen sources in transition-metal-catalyzed synthetic chemistry has been well developed; however, their application as electrophilic sulfur cation surrogates remains uncharted territory. Herein, we report the unexpected discovery that sulfonyl hydrazones serve as programmable sulfur transfer in nickel-catalyzed C–S coupling with a broad range of organic halides. This method forges the nickel catalytic cycle toward selective C–S cross-coupling while effectively suppressing the competing formation of conventional C–C coupling products. Mechanistic studies indicate that the success of this strategy stems from the favorable reduction potential imparted by the electron-withdrawing SO2R group, which enables manganese to reduce the hydrazones in situ, generating key electrophilic sulfur species to engage in a distinctive nickel catalytic cycle that favors C–S over C–C bond formation.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"215 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111284","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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
H-Bond- and Strain-Release-Guided Photoreaction of Alkenes, p-Quinone Methides, and Ammonium Thiocyanate 烯烃、对醌类和硫氰酸铵的氢键和菌株释放光化学反应
IF 5.2 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-02 DOI: 10.1021/acs.orglett.5c05458
Jobsy Jose,Arun Yadav,Saumya Singh,Sathish Kumar Mudedla,Chandra Bhushan Tripathi
Spiro-cyclobutanes are sp3-rich molecules with applications in synthetic chemistry and drug discovery. The existing literature focuses mainly on their synthesis via the metal-catalyzed functionalization of substrates, such as spiro-cyclobutenes. In this letter, we disclose a H-bond-directed photochemical synthesis of densely substituted spiro-cyclobutanes. Moreover, a strain-release- and H-bond-directed three-component reaction of alkenes, p-quinone methide, and NH4SCN is also discussed. The reaction outcome is explained through control experiments and DFT calculations.
螺环丁烷是一种富含sp3的分子,在合成化学和药物发现方面有着广泛的应用。现有的文献主要集中在通过金属催化的底物功能化合成它们,如螺环丁烯。在这封信中,我们披露了一个h键导向的光化学合成密集取代螺环丁烷。此外,还讨论了一种以菌株释放和氢键为导向的烯烃、对醌和NH4SCN的三组分反应。通过控制实验和DFT计算对反应结果进行了解释。
{"title":"H-Bond- and Strain-Release-Guided Photoreaction of Alkenes, p-Quinone Methides, and Ammonium Thiocyanate","authors":"Jobsy Jose,Arun Yadav,Saumya Singh,Sathish Kumar Mudedla,Chandra Bhushan Tripathi","doi":"10.1021/acs.orglett.5c05458","DOIUrl":"https://doi.org/10.1021/acs.orglett.5c05458","url":null,"abstract":"Spiro-cyclobutanes are sp3-rich molecules with applications in synthetic chemistry and drug discovery. The existing literature focuses mainly on their synthesis via the metal-catalyzed functionalization of substrates, such as spiro-cyclobutenes. In this letter, we disclose a H-bond-directed photochemical synthesis of densely substituted spiro-cyclobutanes. Moreover, a strain-release- and H-bond-directed three-component reaction of alkenes, p-quinone methide, and NH4SCN is also discussed. The reaction outcome is explained through control experiments and DFT calculations.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"292 1","pages":""},"PeriodicalIF":5.2,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098070","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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
Stereoselective Synthesis of the Western Fragment of Vancoresmycin. 万古霉素西片段的立体选择性合成。
IF 5 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-02 DOI: 10.1021/acs.orglett.6c00073
Max Schönenbroicher, Maximilian Seul, Simon Morgenschweis, Florian Heppner, Dirk Menche

The synthesis of the western fragment of vancoresmycin was accomplished in a highly modular and stereoselective manner. Central to this strategy was a modified Cu-catalyzed β-boration protocol for α,β-unsaturated enones, which enabled convergent construction of complex, densely functionalized polyketide architectures with high stereocontrol. Application to a structurally demanding fragment highlighted its potential as a general tool for 1,3-diol construction. In addition, NMR comparison confirmed the stereochemical assignment of the western part of vancoresmycin.

万古霉素西部片段的合成以高度模块化和立体选择性的方式完成。该策略的核心是改进的cu催化α,β-不饱和烯酮的β-硼化协议,这使得具有高立体控制的复杂,密集功能化的聚酮结构的聚合构建成为可能。应用于结构要求高的片段突出了其作为1,3-二醇构建的通用工具的潜力。此外,核磁共振对比证实了万古霉素西部的立体化学定位。
{"title":"Stereoselective Synthesis of the Western Fragment of Vancoresmycin.","authors":"Max Schönenbroicher, Maximilian Seul, Simon Morgenschweis, Florian Heppner, Dirk Menche","doi":"10.1021/acs.orglett.6c00073","DOIUrl":"https://doi.org/10.1021/acs.orglett.6c00073","url":null,"abstract":"<p><p>The synthesis of the western fragment of vancoresmycin was accomplished in a highly modular and stereoselective manner. Central to this strategy was a modified Cu-catalyzed β-boration protocol for α,β-unsaturated enones, which enabled convergent construction of complex, densely functionalized polyketide architectures with high stereocontrol. Application to a structurally demanding fragment highlighted its potential as a general tool for 1,3-diol construction. In addition, NMR comparison confirmed the stereochemical assignment of the western part of vancoresmycin.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":" ","pages":""},"PeriodicalIF":5.0,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146103146","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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
期刊
Organic Letters
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