Pub Date : 2024-10-22DOI: 10.1016/j.tet.2024.134324
Ren-Yu Tian , Mohammad Sanayi Haqmal , Yu-Ting Bao , Shi-Yao Liu , Guang-Ying Chen , Li Tang
Beckmann rearrangement, a classical reaction of introducing nitrogen to carbon skeleton compounds for amide synthesis, is widely used in academia and industry. Herein, an electrochemical Beckmann rearrangement is reported, utilizing 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) as a mediator to prevent the over-electro-oxidation of products, which could afford amide in excellent yield.
{"title":"Amide synthesis from DDQ-mediated electrochemical Beckmann rearrangement","authors":"Ren-Yu Tian , Mohammad Sanayi Haqmal , Yu-Ting Bao , Shi-Yao Liu , Guang-Ying Chen , Li Tang","doi":"10.1016/j.tet.2024.134324","DOIUrl":"10.1016/j.tet.2024.134324","url":null,"abstract":"<div><div>Beckmann rearrangement, a classical reaction of introducing nitrogen to carbon skeleton compounds for amide synthesis, is widely used in academia and industry. Herein, an electrochemical Beckmann rearrangement is reported, utilizing 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) as a mediator to prevent the over-electro-oxidation of products, which could afford amide in excellent yield.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"168 ","pages":"Article 134324"},"PeriodicalIF":2.1,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142533898","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
An approach towards the synthesis of novel isosteres of benzonaphthyridines and benzonaphthonaphthyridines from the condensation reaction between 4-chloro-2-methylquinolines/4-chloro-2-methylbenzo[h]quinoline and appropriate o-amino aromatic and heteroaromatic carboxylic acids by using solvent (ethanol)/solvent free (neat) condition to yield the intermediate followed by the cyclization with PPA. The intermediate yield has been slightly increased in neat (solvent-free) conditions compared to solvent conditions. Further, the target isosteres of benzonaphthyridines and benzonaphthonaphthyridines were achieved in the one-pot synthesis using a CuI catalyst with a higher yield than the stepwise method. Quantum chemical calculations of synthesized compounds are performed by using M06-2X with 6-311+G(d,p) basis set in water, DFT calculations of the molecular electrostatic potential (MEP), frontier molecular orbitals (FMOs), and the optimized geometry of the XRD values are compared with experimental values. All the synthesized novel isosteres molecules are investigated under molecular docking studies using MMP1 and MMP2 proteins, which showed all the molecules have the potential to heal pancreatic cancer. The most potent molecules among them are 3i and 3h due to their better docking scores. Furthermore, the molecules' pharmacokinetic (ADME) parameters have been observed to be effective in future biological evaluations of these compounds to be active.
{"title":"Synthesis of novel isostere analogues of naphthyridines using CuI catalyst: DFT computations (FMO, MEP), molecular docking and ADME analysis","authors":"Kolandaivel Prabha , Satheeshkumar Rajendran , Balasubramanian Mythili Gnanamangai , Balachandra Mohan J , Koray Sayin , K.J. Rajendra Prasad , Gamze Tüzün","doi":"10.1016/j.tet.2024.134323","DOIUrl":"10.1016/j.tet.2024.134323","url":null,"abstract":"<div><div>An approach towards the synthesis of novel isosteres of benzonaphthyridines and benzonaphthonaphthyridines from the condensation reaction between 4-chloro-2-methylquinolines/4-chloro-2-methylbenzo[<em>h</em>]quinoline and appropriate <em>o</em>-amino aromatic and heteroaromatic carboxylic acids by using solvent (ethanol)/solvent free (neat) condition to yield the intermediate followed by the cyclization with PPA. The intermediate yield has been slightly increased in neat (solvent-free) conditions compared to solvent conditions. Further, the target isosteres of benzonaphthyridines and benzonaphthonaphthyridines were achieved in the one-pot synthesis using a CuI catalyst with a higher yield than the stepwise method. Quantum chemical calculations of synthesized compounds are performed by using M06-2X with 6-311+G(d,p) basis set in water, DFT calculations of the molecular electrostatic potential (MEP), frontier molecular orbitals (FMOs), and the optimized geometry of the XRD values are compared with experimental values. All the synthesized novel isosteres molecules are investigated under molecular docking studies using MMP1 and MMP2 proteins, which showed all the molecules have the potential to heal pancreatic cancer. The most potent molecules among them are <strong>3i</strong> and <strong>3h</strong> due to their better docking scores. Furthermore, the molecules' pharmacokinetic (ADME) parameters have been observed to be effective in future biological evaluations of these compounds to be active.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"168 ","pages":"Article 134323"},"PeriodicalIF":2.1,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142533895","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-22DOI: 10.1016/j.tet.2024.134322
Xiaopei Chen , Zhiwei Ma , Chuanchuan Wang, Xuehui Hou, Juntao Liu
A facile and efficient protocol for Ir(III)-catalyzed ortho-alkenylation and annulation of N-iminopyridinium ylides with acrylates and alkynes has been developed, providing o-alkenyl benzamides and isoquinolones in good to excellent yields. This reaction proceeds well under external oxidant free conditions with high practicality and efficiency, and broad functional group tolerance.
{"title":"Ir(III)-catalyzed C–H alkenylation/annulation of N-iminopyridinium ylides with acrylates and alkynes","authors":"Xiaopei Chen , Zhiwei Ma , Chuanchuan Wang, Xuehui Hou, Juntao Liu","doi":"10.1016/j.tet.2024.134322","DOIUrl":"10.1016/j.tet.2024.134322","url":null,"abstract":"<div><div>A facile and efficient protocol for Ir(III)-catalyzed ortho-alkenylation and annulation of N-iminopyridinium ylides with acrylates and alkynes has been developed, providing o-alkenyl benzamides and isoquinolones in good to excellent yields. This reaction proceeds well under external oxidant free conditions with high practicality and efficiency, and broad functional group tolerance.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"168 ","pages":"Article 134322"},"PeriodicalIF":2.1,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142533901","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Heavy metal pollutants, such as Pb2+ ions, pose a substantial hazard to human health and ecosystems, and it was of great significance to develop cost-effective and portable techniques for online and visual detection of Pb2+. Herein, we fabricated a novel chromogenic and fluorogenic dual-channel sensor NQA through a Schiff base reaction involving a dicyanoisophorone derivative and isoniazid, enabling effective detection of Pb2+ ions. Upon complexation with Pb2+ ions at a 1:1 M ratio, the fluorescence intensity of NQA exhibited a remarkable enhancement. The naked-eye colorimetric detection utilizing NQA demonstrated a distinct color change to specific Pb2+ ions concentration from yellow to light pink. Based on this principle, a smartphone-assisted sensing platform was developed for visual and high-quality identification of Pb2+ in real samples. The UV binding constant for Pb2+ ions was determined to be 1.84 × 105 M−1, with a detection limit of 0.38 μM. Furthermore, the versatility of NQA extended to applications in naked-eye test paper experiments, the detection of Pb2+ ions in real water samples and living cells, showcasing its potential for environmental and biological monitoring.
{"title":"A smartphone-assisted chromogenic and fluorogenic dual-channel sensor for specific determination of toxic Pb2+ ions with multifaceted applications","authors":"Haiyan Xu , Wenlong Qin , Junyu Zhu , Ying-Guo Liu","doi":"10.1016/j.tet.2024.134316","DOIUrl":"10.1016/j.tet.2024.134316","url":null,"abstract":"<div><div>Heavy metal pollutants, such as Pb<sup>2+</sup> ions, pose a substantial hazard to human health and ecosystems, and it was of great significance to develop cost-effective and portable techniques for online and visual detection of Pb<sup>2+</sup>. Herein, we fabricated a novel chromogenic and fluorogenic dual-channel sensor <strong>NQA</strong> through a Schiff base reaction involving a dicyanoisophorone derivative and isoniazid, enabling effective detection of Pb<sup>2+</sup> ions. Upon complexation with Pb<sup>2+</sup> ions at a 1:1 M ratio, the fluorescence intensity of <strong>NQA</strong> exhibited a remarkable enhancement. The naked-eye colorimetric detection utilizing <strong>NQA</strong> demonstrated a distinct color change to specific Pb<sup>2+</sup> ions concentration from yellow to light pink. Based on this principle, a smartphone-assisted sensing platform was developed for visual and high-quality identification of Pb<sup>2+</sup> in real samples. The UV binding constant for Pb<sup>2+</sup> ions was determined to be 1.84 × 10<sup>5</sup> M<sup>−1</sup>, with a detection limit of 0.38 μM. Furthermore, the versatility of <strong>NQA</strong> extended to applications in naked-eye test paper experiments, the detection of Pb<sup>2+</sup> ions in real water samples and living cells, showcasing its potential for environmental and biological monitoring.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"168 ","pages":"Article 134316"},"PeriodicalIF":2.1,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142533897","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-20DOI: 10.1016/j.tet.2024.134315
Hang Gong , Hongmei Fu , Chao Lu , Changqun Cai
An electrochemical decarbonylation of DMF to achieve N,N-dimethyl amino radical and denitrification of sulfonyl hydrazide to achieve sulfonyl radical in the absence of transition metal and additional oxidant was reported here. Signifyingly, cross-coupling reaction rather than homocoupling reactions completely prevail in competition to obtain sulfonamides, which usually exist as skeletons of pharmaceuticals. This work provides a new method for cracking DMF into N,N-dimethylamino radical, and found a value-added application of this industrialized bulk chemical to the synthesis of sulfonamides.
{"title":"Electro-promoted radical-radical cross-coupling reaction to synthesize sulfonamides","authors":"Hang Gong , Hongmei Fu , Chao Lu , Changqun Cai","doi":"10.1016/j.tet.2024.134315","DOIUrl":"10.1016/j.tet.2024.134315","url":null,"abstract":"<div><div>An electrochemical decarbonylation of DMF to achieve <em>N,N</em>-dimethyl amino radical and denitrification of sulfonyl hydrazide to achieve sulfonyl radical in the absence of transition metal and additional oxidant was reported here. Signifyingly, cross-coupling reaction rather than homocoupling reactions completely prevail in competition to obtain sulfonamides, which usually exist as skeletons of pharmaceuticals. This work provides a new method for cracking DMF into <em>N,N</em>-dimethylamino radical, and found a value-added application of this industrialized bulk chemical to the synthesis of sulfonamides.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"168 ","pages":"Article 134315"},"PeriodicalIF":2.1,"publicationDate":"2024-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142533892","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-19DOI: 10.1016/j.tet.2024.134305
Fermín Flores-Manuel , Gabriel Guerrero-Luna , Israel Quiroga-Montes , Kenia Salvador-Atonal , Amairani Domínguez-Bahena , Maura Cárdenas-García , María Guadalupe Hernández-Linares
Hydrazone derivatives were synthesized in a three-step process starting from diosgenin and then tested for their anabolic activity. Through in silico analysis, we identified proteins associated with muscle growth to elucidate the plausible mechanisms and interactions between these compounds and the active site amino acids, thereby providing a rationale for the observed biological results. The results of the in vitro assay on the human skeletal muscle cell line showed an increase in the number of viable cells, which was determined using increasing concentrations of each compound through the XTT assay. Additionally, the increase in protein concentration was measured using the Bradford method. The experimental evaluation revealed that all compounds have differences in increased protein/cell percentage compared to the control and testosterone, which suggests a hyperplastic/hypertrophic effect with a normal morphology.
{"title":"Steroid-based hydrazones as anabolic agents: Design, synthesis, computational studies, and biological evaluation in human skeletal muscle cell line","authors":"Fermín Flores-Manuel , Gabriel Guerrero-Luna , Israel Quiroga-Montes , Kenia Salvador-Atonal , Amairani Domínguez-Bahena , Maura Cárdenas-García , María Guadalupe Hernández-Linares","doi":"10.1016/j.tet.2024.134305","DOIUrl":"10.1016/j.tet.2024.134305","url":null,"abstract":"<div><div>Hydrazone derivatives were synthesized in a three-step process starting from diosgenin and then tested for their anabolic activity. Through <em>in silico</em> analysis, we identified proteins associated with muscle growth to elucidate the plausible mechanisms and interactions between these compounds and the active site amino acids, thereby providing a rationale for the observed biological results. The results of the <em>in vitro</em> assay on the human skeletal muscle cell line showed an increase in the number of viable cells, which was determined using increasing concentrations of each compound through the XTT assay. Additionally, the increase in protein concentration was measured using the Bradford method. The experimental evaluation revealed that all compounds have differences in increased protein/cell percentage compared to the control and testosterone, which suggests a hyperplastic/hypertrophic effect with a normal morphology.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"168 ","pages":"Article 134305"},"PeriodicalIF":2.1,"publicationDate":"2024-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142533201","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-18DOI: 10.1016/j.tet.2024.134306
Bin Guo , Jing Zhang , Dan Chen , David J. Young , Hong-Xi Li
Transition metal catalyzed direct olefination of alkyl heteroarenes with alcohols using acceptorless dehydrogenative coupling (ADC) reactions and aerobic oxidative olefination are effective, versatile transformations for the construction of alkenyl heterocyclic compounds. Various transition metal catalysts based on noble metals (Ru) and their earth-abundant equivalents (Mn, Ni, Fe, Co) have been employed for these protocols. Water and hydrogen are the only byproducts and the starting alcohols are less toxic, more readily available, more easily handled and more atom economical than their halogen counterparts. This review details recent advances in these green methodologies, describing scope, reaction mechanisms, chemo-selectivity and applications in synthesis.
{"title":"Transition metal-catalyzed olefination of alkyl heteroarenes with alcohols","authors":"Bin Guo , Jing Zhang , Dan Chen , David J. Young , Hong-Xi Li","doi":"10.1016/j.tet.2024.134306","DOIUrl":"10.1016/j.tet.2024.134306","url":null,"abstract":"<div><div>Transition metal catalyzed direct olefination of alkyl heteroarenes with alcohols using acceptorless dehydrogenative coupling (ADC) reactions and aerobic oxidative olefination are effective, versatile transformations for the construction of alkenyl heterocyclic compounds. Various transition metal catalysts based on noble metals (Ru) and their earth-abundant equivalents (Mn, Ni, Fe, Co) have been employed for these protocols. Water and hydrogen are the only byproducts and the starting alcohols are less toxic, more readily available, more easily handled and more atom economical than their halogen counterparts. This review details recent advances in these green methodologies, describing scope, reaction mechanisms, chemo-selectivity and applications in synthesis.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"168 ","pages":"Article 134306"},"PeriodicalIF":2.1,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142533202","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-18DOI: 10.1016/j.tet.2024.134300
Lucero Díaz-Peralta , Mario Fernandez-Zertuche , Juan Alberto Guevara-Salazar , Jessica R. Moran-Diaz , Luis Eduardo Hernandez-Dominguez , Rodrigo Said Razo-Hernández
We report the synthesis of a new series of γ-aminobutyric acid (GABA) analogues as possible GABA-AT inhibitors, where the nitrogen at the Ƴ-position is contained in a 1,5-disubstituted-1,2,3-triazole ring system. The triazole ring system was assembled by the Ru(I)-catalyzed alkyne-azide 1,3-dipolar cycloaddition (RuACC) protocol. GABA-AT inhibition activity was predicted by means of a QSAR model that was constructed in this work. Different molecular descriptors families were employed for its construction, like steric type ( and ), solubility type (), and electronic type (). Additionally, a similarity analysis based on the electronic profile of 1,5-triazole and 1,4-triazole GABA analogues was done to support the QSAR predictions. Finally, the three best candidates were biologically tested as Pseudomonas fluorescens GABA-AT inhibitors showing an inhibition percent compared to FDA approved inhibitors.
{"title":"1,5-Disubstituted-1,2,3-Triazoles as GABA analogues: Synthesis, QSAR and biological evaluation as Pseudomonas fluorescens GABA-AT inhibitors","authors":"Lucero Díaz-Peralta , Mario Fernandez-Zertuche , Juan Alberto Guevara-Salazar , Jessica R. Moran-Diaz , Luis Eduardo Hernandez-Dominguez , Rodrigo Said Razo-Hernández","doi":"10.1016/j.tet.2024.134300","DOIUrl":"10.1016/j.tet.2024.134300","url":null,"abstract":"<div><div>We report the synthesis of a new series of γ-aminobutyric acid (GABA) analogues as possible GABA-AT inhibitors, where the nitrogen at the Ƴ-position is contained in a 1,5-disubstituted-1,2,3-triazole ring system. The triazole ring system was assembled by the Ru(I)-catalyzed alkyne-azide 1,3-dipolar cycloaddition (RuACC) protocol. GABA-AT inhibition activity was predicted by means of a QSAR model that was constructed in this work. Different molecular descriptors families were employed for its construction, like steric type (<span><math><mrow><mi>W</mi><mi>a</mi><mi>p</mi></mrow></math></span> and <span><math><mrow><mi>P</mi><mi>W</mi><mn>5</mn></mrow></math></span>), solubility type (<span><math><mrow><mo>Δ</mo><mtext>PSA</mtext></mrow></math></span>), and electronic type (<span><math><mrow><mo>Δ</mo><msub><mrow><mi>T</mi><mi>r</mi><mi>i</mi><mi>a</mi><mi>z</mi><mi>o</mi><mi>l</mi><mi>e</mi></mrow><mn>3</mn></msub></mrow></math></span>). Additionally, a similarity analysis based on the electronic profile of 1,5-triazole and 1,4-triazole GABA analogues was done to support the QSAR predictions. Finally, the three best candidates were biologically tested as <em>Pseudomonas fluorescens</em> GABA-AT inhibitors showing an inhibition percent compared to FDA approved inhibitors.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"168 ","pages":"Article 134300"},"PeriodicalIF":2.1,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142533203","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-11DOI: 10.1016/j.tet.2024.134302
Arunava Misra, Mohabul Alam Mondal
One-pot synthesis of isoindoloindonoles having various auxochrome, from easily available starting materials phthalaldehyde and o-aminochalcone, involving palladium(II) acetate catalysis in acetic acid is reported. A mechanism based on the formation of 2-aryl-2H-isoindol-1-ol (22) intermediate is proposed for the formation of the tetracyclic core of isoindoloindonoles. The possible intramolecular cyclization via the direct participation of the carbonyl vs the adjacent αβ-conjugated double bond was evaluated. Thus, a detailed study on how the presence of electronically different groups at the β position of chalcones affects the outcome of the cyclization reaction and the photophysical properties of the resulting isoindoloindolones is presented here. Furthermore, the core structure was determined using NMR, mass and single-crystal X-ray diffraction analysis.
本研究报道了在乙酸中通过乙酸钯（II）催化，从易于获得的起始原料邻苯二甲醛和邻氨基查尔酮出发，一步法合成具有各种辅助色素的异吲哚吲哚类化合物。提出了一种基于 2-芳基-2H-异吲哚-1-醇 (22) 中间体形成的机制，用于形成异吲哚酮类化合物的四环核心。通过羰基与邻近的 αβ 共轭双键的直接参与，对分子内环化的可能性进行了评估。因此，本文详细研究了在查耳酮的 β 位上存在电子不同的基团如何影响环化反应的结果以及所得异吲哚吲哚酮的光物理特性。此外，还利用核磁共振、质量和单晶 X 射线衍射分析确定了核心结构。
{"title":"Assembling phthalaldehyde and o-aminochalcones by Pd(II) catalyzed tandem reaction for synthesizing isoindoloindonole fluorophores","authors":"Arunava Misra, Mohabul Alam Mondal","doi":"10.1016/j.tet.2024.134302","DOIUrl":"10.1016/j.tet.2024.134302","url":null,"abstract":"<div><div>One-pot synthesis of isoindoloindonoles having various auxochrome, from easily available starting materials phthalaldehyde and <em>o</em>-aminochalcone, involving palladium(II) acetate catalysis in acetic acid is reported. A mechanism based on the formation of 2-aryl-2<em>H</em>-isoindol-1-ol (<strong>22</strong>) intermediate is proposed for the formation of the tetracyclic core of isoindoloindonoles. The possible intramolecular cyclization via the direct participation of the carbonyl vs the adjacent αβ-conjugated double bond was evaluated. Thus, a detailed study on how the presence of electronically different groups at the β position of chalcones affects the outcome of the cyclization reaction and the photophysical properties of the resulting isoindoloindolones is presented here. Furthermore, the core structure was determined using NMR, mass and single-crystal X-ray diffraction analysis.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"167 ","pages":"Article 134302"},"PeriodicalIF":2.1,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142433603","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Visible-light-mediated metal-free cyclopropanation reaction of diazo compounds with different olefins or arenes have been fully developed in recent years. However, electron-deficient olefins still could not be well tolerated in these reactions. Here, by using 3-diazooxindole as the carbene precursor, the visible-light-mediated cyclopropanation reaction of diazo compounds with electron-deficient olefins was successfully developed. The electron-rich olefins were also well tolerated in the reactions. A series of spirocyclopropyloxindoles were synthesized in moderate to high yields under mild, metal-free conditions. Mechanism studies reveal that both singlet and triplet carbenes are probably involved in the reaction.
{"title":"Visible-light-mediated cyclopropanation reactions of 3-diazooxindoles with olefins","authors":"Zhuangzhuang Mu, Haochi Xie, Shundong Gan, Hujin Li, Yanan Hou, Mingcheng Qian, Shuai Zhao, Xin Chen","doi":"10.1016/j.tet.2024.134296","DOIUrl":"10.1016/j.tet.2024.134296","url":null,"abstract":"<div><div>Visible-light-mediated metal-free cyclopropanation reaction of diazo compounds with different olefins or arenes have been fully developed in recent years. However, electron-deficient olefins still could not be well tolerated in these reactions. Here, by using 3-diazooxindole as the carbene precursor, the visible-light-mediated cyclopropanation reaction of diazo compounds with electron-deficient olefins was successfully developed. The electron-rich olefins were also well tolerated in the reactions. A series of spirocyclopropyloxindoles were synthesized in moderate to high yields under mild, metal-free conditions. Mechanism studies reveal that both singlet and triplet carbenes are probably involved in the reaction.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"167 ","pages":"Article 134296"},"PeriodicalIF":2.1,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142433604","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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