The Journal of Organic Chemistry最新文献

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Biaryl Anion Radical Formation by Potassium Metal Reduction of Aryl Isocyanates and Triaryl Isocyanurates 金属钾还原芳基异氰酸酯和三芳基异氰酸酯形成的双芳基阴离子自由基

IF 4.354 2区化学 Q1 CHEMISTRY, ORGANIC

The Journal of Organic Chemistry

Pub Date : 2024-10-13 DOI: 10.1021/acs.joc.4c01844

Steven J. Peters, Sean H. Kennedy, Colton J. Christiansen

The potassium metal reduction of aryl isocyanates (aryl = phenyl, p-tolyl, 3,5-dimethylphenyl, 4-biphenylyl, and 1-naphthyl) in THF with 18-crown-6 or in HMPA results in the formation of the corresponding triaryl isocyanurate anion radicals. Continued exposure to potassium results in loss of the isocyanurate anion radical and the eventual formation of the respective biaryl anion radical. The 1,1′-binaphthyl anion radical is found to undergo a cyclodehydrogenation reaction, which leads to formation of the perylene anion radical. When authentic triaryl isocyanurates are reduced with metal, the heterocyclic ring undergoes fragmentation with elimination of carbon monoxide to produce a triarylbiuret dianion. This ring opening reaction is initiated by the two-electron reduction of the neutral isocyanurate species. The biaryl anion radical is formed when the biuret dianion is reduced further with metal. A possible mechanism for biaryl formation involves a heterolytic cleavage of an aryl C–N bond and release of an aryl radical once the triarylbiuret dianion is further reduced. A subsequent intermolecular reaction between two aryl radicals forms the corresponding biaryl, which can then be reduced to the anion radical. Notably, when a mixture of two different triaryl isocyanurate compounds is reduced in solution, the corresponding mixed biaryl anion radical is generated.

芳基异氰酸酯（芳基=苯基、对甲苯基、3,5-二甲基苯基、4-联苯基和 1-萘基）在 THF 中与 18-冠醚-6 或在 HMPA 中发生金属钾还原反应后，会形成相应的三芳基异氰脲酸酯阴离子自由基。继续与钾接触会导致异氰脲酸酯阴离子自由基的损失，最终形成相应的双芳基阴离子自由基。1,1′-联萘阴离子自由基会发生环氢化反应，从而形成过烯阴离子自由基。当正宗的三芳基异氰尿酸酯被金属还原时，杂环会随着一氧化碳的消除而发生破碎，生成三芳基双脲醛二阴离子。这种开环反应是由中性异氰尿酸盐的双电子还原反应引发的。双芳烷基阴离子在金属的作用下进一步还原，就形成了双芳烷基阴离子自由基。双芳基形成的一种可能机制是，一旦三芳基双脲酸酯二元离子被进一步还原，芳基 C-N 键就会发生异性裂解，并释放出芳基自由基。随后，两个芳基之间发生分子间反应，形成相应的双芳基，然后再还原成阴离子基。值得注意的是，当两种不同的三芳基异氰尿酸酯化合物的混合物在溶液中被还原时，就会生成相应的混合双芳基阴离子自由基。

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引用次数: 0

Palladium-Catalyzed Annulation Reaction of Bay-Diiodinated Arenes with o-Chloroaromatic Carboxylic Acids to Access Polycyclic Aromatic Compounds 钯催化湾二碘化烯与邻氯芳香族羧酸的环化反应以获得多环芳香族化合物

IF 4.354 2区化学 Q1 CHEMISTRY, ORGANIC

The Journal of Organic Chemistry

Pub Date : 2024-10-13 DOI: 10.1021/acs.joc.4c01785

Song Li, Cheng-Rong Cui, Na Huang, Bi-Qin Wang, Chun Feng, Yingbo Shi, Shi-Kai Xiang

A palladium-catalyzed annulation reaction of bay-diiodinated arenes with o-chloroaromatic carboxylic acids was established. This approach enables the synthesis of a variety of polycyclic aromatic compounds, especially polyalkoxy-substituted polycyclic aromatic compounds, frequently found in discotic liquid-crystalline materials. The investigations indicate that the product 2,3,8,9,12,13-hexakis(hexyloxy)-5-azadibenzo[fg,op]tetracene demonstrates favorable room-temperature liquid-crystalline properties.

建立了一种钯催化的垸基二碘化烷与邻氯芳香族羧酸的环化反应。这种方法可以合成多种多环芳烃化合物，尤其是在盘状液晶材料中经常出现的多烷氧基取代的多环芳烃化合物。研究表明，产物 2,3,8,9,12,13-hexakis(hexyloxy)-5-azadibenzo[fg,op]tetracene 具有良好的室温液晶特性。

引用次数: 0

TMSCl-Promoted Sulfonylation of Propargylic Alcohols with Sodium Sulfinates for the Construction of (E)-1,3-Disulfonylpropenes and (E)-1-Sulfonylpropenols TMSCl 促进丙炔醇与硫酸钠的磺酰化反应以构建 (E)-1,3-二磺酰基丙烯和 (E)-1-磺酰基丙烯醇

IF 4.354 2区化学 Q1 CHEMISTRY, ORGANIC

The Journal of Organic Chemistry

Pub Date : 2024-10-12 DOI: 10.1021/acs.joc.4c01829

Shimin Jiang, Meng Liang, Xi Chen, Ruchun Yang, Hai-Xin Ding, Mu-Jia Luo, Haiyang Huang, Xian-Rong Song, Qiang Xiao

A direct and novel transformation of propargylic alcohols with sodium sulfinates for the regio- and stereoselective synthesis of (E)-1,3-disulfonylpropenes and (E)-1-sulfonylpropenols was successfully developed in the presence of TMSCl under mild conditions. The preliminary mechanistic experiments demonstrated that the reaction underwent an unprecedented dual nucleophilic substitution/radical addition process, in which sodium sulfinates were used not only as nucleophiles but also as a sulfonyl radical source.

在 TMSCl 存在的温和条件下，成功开发了一种丙炔醇与亚磺酸钠直接转化的新方法，用于区域和立体选择性合成 (E)-1,3-二磺酰基丙烯和 (E)-1-磺酰基丙烯醇。初步的机理实验表明，该反应经历了一个前所未有的亲核取代/自由基加成双重过程，其中亚磺酸钠不仅被用作亲核物，还被用作磺酰基自由基源。

引用次数: 0

Photoredox-Catalyzed Alkynylation of C(sp3)-H Bonds Adjacent to a Nitrogen Atom of Tertiary Amines with Alkynyl Bromides 光氧化催化炔溴化物与叔胺氮原子邻接的 C（sp3）-H 键的炔化反应

IF 4.354 2区化学 Q1 CHEMISTRY, ORGANIC

The Journal of Organic Chemistry

Pub Date : 2024-10-12 DOI: 10.1021/acs.joc.4c02065

Jin-Long Dai, Tao Wang, Yan Hao, Yue Zhang, Shenghu Yan, Guigen Li, Jia-Yin Wang

A novel and robust alkynylation of C(sp³)–H bonds adjacent to a nitrogen atom of tertiary amines with alkynyl bromides as radical alkynylating reagents has been realized under visible-light irradiation. A range variety of tertiary amines including N-arylamines and N-alkylamine have been coupled with both aromatic and aliphatic alkynyl bromides to furnish 51 examples of propargylamines in moderate to excellent yields (31–80% yields). The possible mechanism was a radical addition–elimination process based on preliminary mechanistic studies.

在可见光辐照下，以炔基溴化物作为自由基炔化试剂，对邻近叔胺氮原子的 C(sp3)-H键进行了一种新颖而稳健的炔化反应。包括 N-芳基胺和 N-烷基胺在内的各种叔胺与芳香族和脂肪族溴化炔基化合物发生偶联反应，以中等到极好的收率（31-80% 的收率）制备出 51 种丙炔基胺。根据初步的机理研究，可能的机理是自由基加成-消除过程。

引用次数: 0

Ph₃P═O-Catalyzed Reductive Deoxygenation of Alcohols. Ph3P═O 催化的醇还原脱氧反应。

IF 3.3 2区化学 Q1 CHEMISTRY, ORGANIC

The Journal of Organic Chemistry

Pub Date : 2024-10-11 DOI: 10.1021/acs.joc.4c01847

Qiang Li, Yu Sun, Mu-Xian Fu, Jin-Hong Lin, Ji-Chang Xiao

Reductive deoxygenation of alcohols is particularly challenging because of the high bond dissociation energy of the C-OH bond and the poor leaving ability of the hydroxyl group. Herein we describe a Ph₃P═O-catalyzed reductive deoxygenation of benzyl alcohols with PhSiH₃ under an air atmosphere within 30 min of reaction time. The use of catalytic loading of Ph₃P═O enhances the practicality of this protocol.

醇类的还原脱氧反应尤其具有挑战性，因为 C-OH 键的键解离能很高，而羟基的离去能力很差。在此，我们介绍了在空气气氛下，用 PhSiH3 在 30 分钟反应时间内催化 Ph3P═O 还原脱氧苯甲醇的方法。利用 Ph3P═O 的催化负载提高了该方案的实用性。

引用次数: 0

Synthesis of 3,3-Disubstituted Thietane Dioxides. 合成 3,3-二取代的硫杂环丁烷二氧化物。

IF 3.3 2区化学 Q1 CHEMISTRY, ORGANIC

The Journal of Organic Chemistry

Pub Date : 2024-10-11 DOI: 10.1021/acs.joc.4c01843

Peerawat Saejong, Jianing Zhong, Juan J Rojas, Andrew J P White, Chulho Choi, James A Bull

4-Membered heterocycles have been increasingly exploited in medicinal chemistry and, as small polar motifs, often show important influence on activity and physicochemical properties. Thietane dioxides similarly offer potential in both agricultural and pharmaceutical applications but are notably understudied. Here we report a divergent approach to 3,3-disubstituted thietane dioxide derivatives by forming carbocations on the 4-membered ring with catalytic Lewis or Brønsted acids. Benzylic tertiary alcohols of the thietane dioxides are coupled directly with arenes, thiols, and alcohols.

4 元杂环在药物化学中的应用日益广泛，作为小极性基团，它们往往对活性和理化性质具有重要影响。硫烷二氧杂环同样具有农业和医药应用潜力，但研究明显不足。在此，我们报告了一种不同的方法，即通过催化路易斯酸或布伦斯特酸在四元环上形成碳基，从而获得 3,3-二取代的二氧化硫烷衍生物。二氧代硫杂环丁烷的苄基叔醇直接与炔烃、硫醇和醇偶联。

引用次数: 0

(E)-Selective Weinreb Amide-Type Horner-Wadsworth-Emmons Reaction: Effect of Reaction Conditions, Substrate Scope, Isolation of a Reactive Magnesium Phosphonoenolate, and Applications. (E)-Selective Weinreb Amide-Type Horner-Wadsworth-Emmons Reaction：反应条件的影响、底物范围、反应性膦酸镁的分离及应用。

IF 3.3 2区化学 Q1 CHEMISTRY, ORGANIC

The Journal of Organic Chemistry

Pub Date : 2024-10-11 DOI: 10.1021/acs.joc.4c01140

Takatsugu Murata, Hisazumi Tsutsui, Isamu Shiina

An ⁱPrMgCl-deprotonating Weinreb amide-type Horner-Wadsworth-Emmons (HWE) reaction was developed, and the effects of diverse reaction conditions, including the base, cation, solvent, and concentration, were investigated to broaden the substrate scope and achieve high (E)-selectivity. The Weinreb amide-type phosphonoenolate generated from ⁱPrMgCl was found to be isolable, stable for at least over a half year, and applicable in the HWE reaction keeping high productivity and selectivity compared with the in situ generated phosphonoenolate. The results prompted us to perform an application study including successive elongation, synthesis of a biscyclopropane, and Weinreb ketone syntheses.

开发了一种 iPrMgCl 去质子化 Weinreb 酰胺型 Horner-Wadsworth-Emmons (HWE) 反应，并研究了碱、阳离子、溶剂和浓度等不同反应条件对扩大底物范围和实现高（E）选择性的影响。结果发现，与原位生成的膦酸烯酸盐相比，由 iPrMgCl 生成的 Weinreb 酰胺型膦酸烯酸盐可分离、稳定至少超过半年，并可用于 HWE 反应，保持较高的生产率和选择性。这些结果促使我们进行了一项应用研究，包括连续延伸、双环丙烷的合成和魏氏酮的合成。

引用次数: 0

Umpolung Approach to Aldol Products via Isoxazoline N-Oxides as Intermediates 以异噁唑啉 N-氧化物为中间体的醛醇产品乌姆波隆法

IF 4.354 2区化学 Q1 CHEMISTRY, ORGANIC

The Journal of Organic Chemistry

Pub Date : 2024-10-11 DOI: 10.1021/acs.joc.4c01671

Pavel Yu. Ushakov, Alexey Yu. Sukhorukov

A two-step umpolung approach to the diastereoselective synthesis of aldols was developed, in which a conjugated nitroalkene is used as the synthetic equivalent of the enolonium cation, while a sulfur ylide acts as the equivalent of the α-carbinol anion. The resulting isoxazoline N-oxides undergo catalytic reductive cleavage to aldols under mild conditions at room temperature and under 1 atm hydrogen pressure. The efficiency of the method was demonstrated by the synthesis of a series of polysubstituted β-hydroxyketones that are difficult to synthesize using the classical aldol reaction. The developed approach allows for the regiodivergent assembly of aldols by selecting a nitroalkene isomer with the appropriate position of the C,C double bond.

我们开发了一种非对映选择性合成醛醇的两步umpolung 方法，其中共轭硝基烯用作烯醇阳离子的合成等效物，而硫酰基则用作α-甲醇阴离子的等效物。生成的异噁唑啉 N-氧化物在室温和 1 atm 氢压的温和条件下催化还原裂解成醛醇。通过合成一系列难以用经典醛醇反应合成的多取代 β-羟基酮，证明了该方法的高效性。所开发的方法通过选择具有适当 C,C 双键位置的硝基烯异构体，实现了醛醇的变构组装。

引用次数: 0

Asymmetric Aza Friedel-Crafts Reaction of 3,4-Dihydroisoquinolines with 1-Naphthols Catalyzed by Chiral Phosphoric Acids. 手性磷酸催化的 3,4-二氢异喹啉与 1-萘酚的不对称 Aza Friedel-Crafts 反应。

IF 3.3 2区化学 Q1 CHEMISTRY, ORGANIC

The Journal of Organic Chemistry

Pub Date : 2024-10-10 DOI: 10.1021/acs.joc.4c01617

Ye Zhang, Qiaoyu Gan, Xujin Zhang, Xiandong Dai, Fanhua Meng, Zhenhua Gao, Yujun Si, Yongbiao Guo

An efficient chiral phosphoric acid-catalyzed asymmetric aza Friedel-Crafts reaction of 3,4-dihydroisoquinolines and 1-naphthols is described. The reaction provides a general method for the synthesis of diverse chiral tetrahydroisoquinoline with 1-naphthol substituents at the C1-position in excellent yields and enantioselectivities. Based on the conducted mechanistic experiments, a plausible catalytic mechanism was proposed. Moreover, the practicability of the reaction is successfully demonstrated by its application on a gram scale.

介绍了一种高效的手性磷酸催化的 3,4-二氢异喹啉和 1-萘酚的不对称氮杂 Friedel-Crafts 反应。该反应为在 C1 位合成具有 1-萘酚取代基的多种手性四氢异喹啉提供了一种通用方法，并具有极佳的产率和对映选择性。根据所进行的机理实验，提出了一种合理的催化机理。此外，该反应在克级规模上的应用也成功证明了其实用性。

引用次数: 0

π-Bond Dissociation Energies: C–C, C–N, and C–O π 键解离能：C-C、C-N 和 C-O

IF 4.354 2区化学 Q1 CHEMISTRY, ORGANIC

The Journal of Organic Chemistry

Pub Date : 2024-10-10 DOI: 10.1021/acs.joc.4c01925

Steven R. Kass

Single, double, and triple bond dissociation energies are useful quantities, but students and practicing chemists commonly do not know representative values or how they are obtained. In this paper, select π-bond energies are provided and general methods for their determination are discussed. Relationships between heats of hydrogenation, bond dissociation energies, and π-bond strengths are also addressed.

单键、双键和三键离解能是有用的量，但学生和实际化学家通常不知道它们的代表值或获取方法。本文提供了部分 π 键能，并讨论了测定它们的一般方法。本文还讨论了氢化热、键解离能和 π 键强度之间的关系。

引用次数: 0

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