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HCl/DMSO/HFIP-Mediated Chlorination of Pyrrolo[2,1-a]isoquinolines and Other Electron-Rich Heteroarenes. HCl/DMSO/HFIP 介导的吡咯并[2,1-a]异喹啉和其他富电子杂环戊烯的氯化反应。
IF 3.3 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-19 Epub Date: 2024-06-26 DOI: 10.1021/acs.joc.4c00151
Jing Zhou, Xiang Huang, Xin Yu, Liu Yang, Jia-Yi Han, Tsesong Lhazom, Hai-Lei Cui

An efficient oxidative chlorination of pyrrolo[2,1-a]isoquinolines has been established using HCl (aq) as the chlorine source and DMSO as the terminal oxidant in HFIP at ambient temperature. A variety of chlorinated pyrrolo[2,1-a]isoquinoline derivatives have been prepared readily in 23 to 99% yields. This chlorination strategy can be expanded to the functionalization of other electron-rich heteroarenes including substituted pyrroles, indoles, and naphthols.

以盐酸(aq)为氯源,以二甲基亚砜(DMSO)为末端氧化剂,在 HFIP 中于常温下对吡咯并[2,1-a]异喹啉进行高效氧化氯化。各种氯化吡咯并[2,1-a]异喹啉衍生物的制备非常容易,收率在 23% 到 99% 之间。这种氯化策略可以扩展到其他富电子杂环戊烯的官能化,包括取代的吡咯、吲哚和萘酚。
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引用次数: 0
Selective N-functionalization of Arylhydrazines with Primary Alcohols and Acids under PPh3/DDQ System. 在 PPh3/DDQ 系统下芳基肼与伯醇和酸的选择性 N-官能化。
IF 3.3 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-19 Epub Date: 2024-06-30 DOI: 10.1021/acs.joc.4c00915
Shubing Shu, Meng Yu, Wenxin Yu, Tao Wang, Zhenming Zhang

We present a PPh3/DDQ-mediated regiospecific selective N-functionalization of arylhydrazines with primary benzylic alcohols and aryl carboxylic acids for the synthesis of N1-benzyl arylhydrazines and N2-acyl arylhydrazines, respectively. This metal- and base-free approach features very short reaction times (about 10 min), broad substrate scope, good functional group tolerance, and mild reaction conditions. Furthermore, N1-benzlated products have also been successfully applied to the concise synthesis of N-substituted indoles and anticancer drug MDM2 inhibitor.

我们介绍了一种 PPh3/DDQ 介导的芳基肼与伯羟基苄醇和芳基羧酸的选择性 N-官能化反应,分别用于合成 N1-苄基芳基肼和 N2-酰基芳基肼。这种不含金属和碱的方法具有反应时间极短(约 10 分钟)、底物范围广、官能团耐受性好以及反应条件温和等特点。此外,N1-苯甲酰化产物还被成功应用于 N-取代吲哚和抗癌药物 MDM2 抑制剂的简易合成。
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引用次数: 0
Organocatalytic Dearomative Spirocyclization Reaction of Enone-Tethered α-and β-Naphthols and Dearomatization Reaction of In Situ Generated Nitro-Olefin-Tethered α-Naphthols. 烯酮系α-萘酚和β-萘酚的有机催化脱芳烃螺环化反应以及原位生成的硝基烯烃系α-萘酚的脱芳烃反应。
IF 3.3 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-19 Epub Date: 2024-06-26 DOI: 10.1021/acs.joc.4c00131
Amit Shikari, Madhur Sharma, Kalishankar Bhattacharyya, Subhas Chandra Pan

Herein, we report a catalytic dearomative spirocyclization reaction of new substrates having aryl/alkyl enone tethered α- and β-naphthols and a dearomatization reaction of in situ generated nitro-olefin-tethered α-naphthols. The spirocarbocycles were obtained in moderate to good yields with high diastereoselectivities. A preliminary catalytic asymmetric variant was reported. A few applications such as hydrogenations and epoxidation reaction have also been demonstrated. Theoretical study has also been performed to understand high diastereoselectivity in the triethylamine catalyzed spirocyclization reaction.

在此,我们报告了一种催化脱芳烃螺环化反应,该反应以芳基/烷基烯酮系α-和β-萘酚为新底物,并对原位生成的硝基烯烃系α-萘酚进行脱芳烃反应。这些螺环以中等至良好的产率和较高的非对映选择性获得。报告了一种初步催化不对称变体。此外,还展示了氢化和环氧化反应等一些应用。此外,还进行了理论研究,以了解三乙胺催化螺环化反应的高非对映选择性。
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引用次数: 0
Synthesis of the ABC Core of Daphniphyllum Alkaloids with a [5-6-7] Azatricyclic Scaffold via Ring Expansion of Azabicyclic and Azatricyclic Building Blocks. 通过氮杂环和氮杂环构件的扩环合成具有 [5-6-7] 氮杂环支架的 Daphniphyllum 生物碱 ABC 核心。
IF 3.3 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-19 Epub Date: 2024-07-01 DOI: 10.1021/acs.joc.4c01090
Clàudia Marquès, David González-Lizana, Faïza Diaba, Josep Bonjoch

The [5-6-7] azatricyclic ABC core, found in several Daphniphyllum alkaloids, has been synthesized through a novel route involving ring expansion of a perhydroindolone to afford the AC ring system and a radical B ring closure as key steps. The level of functionalization of the reported octahydro-1,7-ethanocyclohepta[b]pyrroles suggests that they can serve as valuable building blocks in this alkaloid field. Also reported is the first synthesis of homomorphans by the ring enlargement of 2-azabicyclo[3.3.1]nonanes.

我们通过一条新颖的路线合成了[5-6-7]叠氮环 ABC 核心,该核心存在于几种 Daphniphyllum 生物碱中,其关键步骤包括过氢吲哚酮扩环生成 AC 环系统和自由基 B 环闭合。所报道的八氢-1,7-乙烷环庚烷并[b]吡咯的官能化程度表明,它们可以作为该生物碱领域的重要构建模块。报告还首次通过 2-氮杂双环[3.3.1]壬烷的扩环合成了同构烷。
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引用次数: 0
Asymmetric Cascade Dearomatization-Cyclization Reaction of Tryptamines with β,γ-Alkynyl-α-imino Esters: Access to Hexahydropyrrolo[2,3-b]indole-Containing Tetrasubstituted α-Amino Allenoates. 色胺与 β,γ-炔基-α-亚胺酯的不对称级联去氢-环化反应:获得含六氢吡咯并[2,3-b]吲哚的四代 α-氨基别烯酸酯。
IF 3.3 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-19 Epub Date: 2024-07-03 DOI: 10.1021/acs.joc.4c01021
Chhavi Khajuria, Nidhi Saini, Parbat Subba, Vinod K Singh

An organocatalytic enantio- and diastereoselective synthesis of hexahydropyrrolo[2,3-b]indole-containing tetrasubstituted α-amino allenoates, exhibiting both axial and central chirality, has been accomplished via cascade dearomatization-cyclization reaction. The γ-addition to β,γ-alkynyl-α-imino esters provides a library of densely substituted highly enantioenriched allenes in high yields and excellent stereoselectivities. In addition, the scope of this methodology has been extended to tryptophol as well. A scale-up reaction and synthetic transformations of the products were performed to demonstrate the practical usefulness of this approach.

通过级联脱芳烃-环化反应,有机催化对映和非对映选择性地合成了六氢吡咯并[2,3-b]吲哚-含四取代α-氨基异烯酸酯,该化合物同时表现出轴向和中心手性。β,γ-炔基-α-亚氨基酯的γ-加成反应以高产率和优异的立体选择性提供了一个高对映富集的高取代度烯属化合物库。此外,该方法的范围还扩展到了色酚。为了证明这种方法的实用性,我们对产品进行了放大反应和合成转化。
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引用次数: 0
Synthesis of Unsymmetrical 3,3'-Dialkyloxindole Boronic Esters from 3-Alkylidene-2-oxindoles Enabled by Copper Catalysis. 通过铜催化从 3-亚烷基-2-吲哚合成不对称的 3,3'-二烷基吲哚硼酸酯。
IF 3.3 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-19 Epub Date: 2024-07-06 DOI: 10.1021/acs.joc.4c01326
Pinku Prasad Mondal, Alvin Antony Chungath, Malavika Krishnan, Subham Das, Aarya Mandodi, Basudev Sahoo

We describe a 1,2-alkylboration of 3-alkylidene-2-oxindoles with a diboron reagent and alkyl bromides and iodides enabled by copper/bisphosphine catalysis. This scalable alkylboration method provides facile access to 3,3'-dialkyloxindole boronic esters featuring an all-carbon quaternary stereocenter and an increased F(sp3) fraction. In addition to good functional group tolerance and prolific utilization of drug/pesticide-derived alkyl iodides, the conversion of the C-B bond to a C-C/C-X bond offers further opportunities for structural variation of 3,3'-dialkyloxindoles.

我们介绍了在铜/双膦催化下,用二硼试剂和烷基溴化物和碘化物对 3-亚烷基-2-氧化吲哚进行 1,2-烷基硼化反应的方法。这种可扩展的烷基硼化方法可以方便地获得 3,3'-二烷基吲哚硼酸酯,其特点是具有全碳四元立体中心和更高的 F(sp3)分数。除了良好的官能团耐受性和大量利用源自药物/农药的烷基碘化物之外,将 C-B 键转化为 C-C/C-X 键还为 3,3'-二烷基吲哚的结构变化提供了更多机会。
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引用次数: 0
Dehydrative Alkylation of Phenols with Alcohols via Formation of Triflate. 酚与醇通过形成三氟酸盐进行脱水烷基化反应。
IF 3.3 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-19 Epub Date: 2024-06-25 DOI: 10.1021/acs.joc.4c00561
Shengjun Ni, Fengyan Zhou, Wenzhi Zhang, Jie Ma

An efficient synergistic trityl cation ([Ph3C][B(C6F5)4])/triflic anhydride (Tf2O) catalyzed alkylation of phenols with alcohols is reported. Benefiting from the formation of the triflate in situ, cheap and readily available active alcohols can be used as the alkylating reagents, and the reaction proceeds under mild reaction conditions with a broad substrate scope. This protocol enables the synthesis of ortho-selective phenols and 2,4,6-trisubstitued phenols containing three different alkyl groups. tert-Amyl triflate was synthesized, and mechanistic studies support a triflate-mediated alkylation process.

本研究报道了一种高效协同的三苯甲基阳离子([Ph3C][B(C6F5)4])/三氟酸酐(Tf2O)催化苯酚与醇的烷基化反应。得益于三氟酸酐的原位形成,廉价易得的活性醇可用作烷基化试剂,反应在温和的反应条件下进行,底物范围广泛。该方法可以合成正交选择性苯酚和含有三个不同烷基的 2,4,6- 三取代苯酚。合成了三氟酸叔戊酯,机理研究支持三氟酸叔戊酯介导的烷基化过程。
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引用次数: 0
Palladium-Catalyzed Synthesis of Nitrones Via Redox Cross-Coupling of Nitro Compounds and Alcohols. 钯催化硝基化合物与醇的氧化还原交叉偶联合成硝基化合物。
IF 3.3 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-19 Epub Date: 2024-06-25 DOI: 10.1021/acs.joc.4c00512
Jian Xing, Hong-Yu Tang, Jing-Lin Chen, Zheng Huang, Jun-Jie Liang, Yao-Sheng Quan, Jian-Gang Mao

A novel methodology for the synthesis of nitrones via palladium-catalyzed redox cross-coupling of nitro compounds and alcohols is established. The protocol is a mild, convenient, ligand-free, and scalable synthesis method that can be compatible with various nitro compounds and alcohols. Nitrone is a significant multifunctional platform synthon which can be synthesized directly and efficiently via this tactic from commercially available and cheap raw materials.

通过钯催化硝基化合物和醇的氧化还原交叉偶联,建立了一种合成硝基化合物的新方法。该方法温和、简便、无配体且可扩展,可与各种硝基化合物和醇类兼容。硝酮是一种重要的多功能平台合成物,通过这种方法可以利用市场上廉价的原材料直接高效地合成硝酮。
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引用次数: 0
Organophotocatalyzed Cross Coupling of C- and Si-Radical to Access Dibenzylic Silanes from para-Quinone Methides and Silanecarboxylic Acids. 有机光催化 C- 和 Si-Radical 交叉偶联,从对位醌甲酰胺和硅烷羧酸中获得二苄基硅烷。
IF 3.3 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-19 Epub Date: 2024-06-26 DOI: 10.1021/acs.joc.4c00973
Duo Zhang, Lei Wang, Guodong Zhang

Herein we present a catalytic cross-coupling strategy between C-radicals and Si-radicals, enabling the efficient, gentle, and versatile synthesis of dibenzylic silanes from para-quinone methides and silanecarboxylic acids as the stable silyl radical precursors. The reaction is facilitated by an inexpensive organophotocatalyst and exhibits broad compatibility with various electron-donating and electron-withdrawing functional groups. Notably, mechanistic investigations suggest the involvement of dibenzylic and silyl radicals, underscoring a novel radical coupling mechanism that introduces a fresh perspective on C-Si bond formation.

在此,我们提出了一种 C-自由基与 Si- 自由基之间的催化交叉偶联策略,从而能够以对苯醌甲醚和硅烷羧酸为稳定的硅自由基前体,高效、温和、多用途地合成二苄基硅烷。该反应由一种廉价的有机光催化剂促成,并与各种供电子和吸电子官能团具有广泛的兼容性。值得注意的是,机理研究表明二苄基和硅基自由基参与了该反应,强调了一种新的自由基偶联机理,为 C-Si 键的形成提供了一个全新的视角。
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引用次数: 0
Arylation of Diethyl Acetamidomalonate with Diaryliodonium Salts En Route to α-Arylglycines. 乙酰胺丙二酸二乙酯与二乙基碘鎓盐的芳基化作用,进而生成 α-芳基甘氨酸。
IF 3.3 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2024-07-19 Epub Date: 2024-07-01 DOI: 10.1021/acs.joc.4c00768
Dmitry I Bugaenko, Olga A Tikhanova, Valeriy V Andreychev, Alexander V Karchava

Diethyl acetamidomalonate (DEAM) has been widely used for the synthesis of α-amino acids via C-alkylation under basic conditions followed by hydrolysis/decarboxylation. In contrast, the C-arylation of this reagent remains undeveloped. Herein, we report a novel strategy for the synthesis of racemic α-arylglycines based on the selective arylation of DEAM with diaryliodonium salts under mild, transition metal-free conditions. The reaction features good functional group tolerance and easy scalability and is applicable to the chemoselective C-H-modification of arenes including approved drugs, thus enabling a straightforward approach to complex α-arylglycines that would be challenging to make otherwise.

乙酰氨基丙二酸二乙酯(DEAM)已被广泛用于在碱性条件下通过 C-烷基化反应合成 α-氨基酸,然后再进行水解/脱羧反应。相比之下,该试剂的 C-芳基化技术仍未得到开发。在此,我们报告了一种基于 DEAM 与二芳基碘鎓盐在温和、无过渡金属条件下选择性芳基化合成外消旋 α-芳基甘氨酸的新策略。该反应具有良好的官能团耐受性和易于扩展的特点,适用于包括已批准药物在内的炔类化合物的化学选择性 C-H 改性,从而能够直接获得复杂的 α-芳基甘氨酸,而不使用其他方法则很难获得这种化合物。
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引用次数: 0
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The Journal of Organic Chemistry
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