This Concept outlines an X−H insertion/cyclization cascade (X=heteroatom), a prominent strategy for the assembly of N,O,S-heterocycles from diazo compounds and X−H-tethered precursors. While focusing on the cyclization via an addition to multiple bonds, we have highlighted Michael-type and Conia-ene reactions, aldol condensation, and Mannich reaction as prevalent ring-closing modes.
{"title":"Diazo-Based Construction of Heterocyclic Systems Via a X−H Insertion/Cyclization Cascade","authors":"Ksenia Malkova, Dmitry Dar'in","doi":"10.1002/ejoc.202400909","DOIUrl":"https://doi.org/10.1002/ejoc.202400909","url":null,"abstract":"This Concept outlines an X−H insertion/cyclization cascade (X=heteroatom), a prominent strategy for the assembly of N,O,S-heterocycles from diazo compounds and X−H-tethered precursors. While focusing on the cyclization via an addition to multiple bonds, we have highlighted Michael-type and Conia-ene reactions, aldol condensation, and Mannich reaction as prevalent ring-closing modes.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"15 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142541979","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}
Jie Wang, Shangxi Zhang, Hui Zhang, Yuanyuan Zheng, Lina Liang, Lei Liu
An efficient and generalized pinacol-like rearrangement of tetrathiafulvalene (TTF) derivatives has been achieved using 2, 2, 6, 6-tetramethylpiperidine oxide (TEMPO) as a key reagent, in place of a traditional metal catalyst. Examination of numerous TTF derivatives demonstrates the reaction's exceptional tolerance to a variety of substituents, achieving an overall yield of up to 97%. The optimization of reaction conditions and evaluation of reaction applicability were achieved by varying factors such as the redox potential (E11/2) of the substrate molecule, substituent type, substituent position, number of substituents, and structural symmetry. Additionally, the reaction mechanism was explored using isotopic labeling, real-time monitoring UV-Vis absorption spectroscopy, and X-ray diffraction (XRD) analysis. Specifically, TTF is oxidized to TTF+• by p-toluenesulfonic acid (TsOH·H2O). TTF+• subsequently reacts with TEMPO and H2O to form a pinacol-like intermediate, which undergoes a rearrangement to release a 2, 2, 6, 6-tetramethylpiperidin-1-ol (TEMPOH) molecule, forming the rearranged product as a hydrogenated cation, this intermediate undergoes deprotonation, leading to the formation of the final spiro product. This investigation led to the identification of a class of reactions for the efficient conversion of TTF derivatives into their spiro products via pinacol-like rearrangement reaction.
{"title":"Construction of Spiro Systems from Tetrathiafulvalene Derivatives by a Pinacol-like Rearrangement","authors":"Jie Wang, Shangxi Zhang, Hui Zhang, Yuanyuan Zheng, Lina Liang, Lei Liu","doi":"10.1002/ejoc.202401071","DOIUrl":"https://doi.org/10.1002/ejoc.202401071","url":null,"abstract":"An efficient and generalized pinacol-like rearrangement of tetrathiafulvalene (TTF) derivatives has been achieved using 2, 2, 6, 6-tetramethylpiperidine oxide (TEMPO) as a key reagent, in place of a traditional metal catalyst. Examination of numerous TTF derivatives demonstrates the reaction's exceptional tolerance to a variety of substituents, achieving an overall yield of up to 97%. The optimization of reaction conditions and evaluation of reaction applicability were achieved by varying factors such as the redox potential (E11/2) of the substrate molecule, substituent type, substituent position, number of substituents, and structural symmetry. Additionally, the reaction mechanism was explored using isotopic labeling, real-time monitoring UV-Vis absorption spectroscopy, and X-ray diffraction (XRD) analysis. Specifically, TTF is oxidized to TTF+• by p-toluenesulfonic acid (TsOH·H2O). TTF+• subsequently reacts with TEMPO and H2O to form a pinacol-like intermediate, which undergoes a rearrangement to release a 2, 2, 6, 6-tetramethylpiperidin-1-ol (TEMPOH) molecule, forming the rearranged product as a hydrogenated cation, this intermediate undergoes deprotonation, leading to the formation of the final spiro product. This investigation led to the identification of a class of reactions for the efficient conversion of TTF derivatives into their spiro products via pinacol-like rearrangement reaction.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"1 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556328","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}
A decarboxylative fluoroalkylation of α,β-unsaturated acids was developed by the use of a dual nickel/photoredox catalysis system. The fluoroalkyl radicals are generated from α-CF3 alkyl bromides by nickel-induced single electron transfer (SET) and are subsequently intercepted by a cinnamic acid to forge the targeted C-C bonds. A wide variety of substrates bearing a diverse set of functional groups were compatible with the mild reaction conditions (visible light, room temperature, cheap metal, no strong oxidant or reductant), thus affording trifluoromethyl analogues of α-methylated allylic compounds.
{"title":"Photocatalytic Decarboxylative Fluoroalkylation of α,β-Unsaturated Carboxylic Acids","authors":"xiuling Wang, Yaxing Wu, Songlin Xu, hongmei qu, Chao Chen","doi":"10.1002/ejoc.202401144","DOIUrl":"https://doi.org/10.1002/ejoc.202401144","url":null,"abstract":"A decarboxylative fluoroalkylation of α,β-unsaturated acids was developed by the use of a dual nickel/photoredox catalysis system. The fluoroalkyl radicals are generated from α-CF3 alkyl bromides by nickel-induced single electron transfer (SET) and are subsequently intercepted by a cinnamic acid to forge the targeted C-C bonds. A wide variety of substrates bearing a diverse set of functional groups were compatible with the mild reaction conditions (visible light, room temperature, cheap metal, no strong oxidant or reductant), thus affording trifluoromethyl analogues of α-methylated allylic compounds.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"492 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142541980","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}
In 3/2‐systems, such as the acetate anion H3CαC′OO−, an sp3 center and an sp2 center are connected by a covalent bond. The interaction of threefold and twofold symmetry results in the pyramidalization of the sp2 center during rotation about bond Esp3−Esp2. Rotation angles ψ=0°, ±60°, ±120°, and ±180° account for conformations with a symmetry plane containing the planar sp2 center CαC′OO. However, in all conformations with rotation angles ψ≠0°, ±60°, ±120°, and ±180° this symmetry plane is lost and pyramidalization must occur with maxima at rotation angles ψ=±30°, ±90°, and ±150°, because the two sides of the sp2 center CαC′OO are different. Inevitably, this leads to a pyramidalization/rotation profile θ/ψ with three maxima, three minima, and six zero‐crossings. Thus, myriads of 3/2‐compounds pyramidalize their sp2 centers each moment to the order of about 2° in a coupled pyramidalization/rotation molecular motion independent of energy.
{"title":"The Pyramidalization of sp2 Centers in 3/2‐Systems Is a “Structural Breathing” Independent of Energy","authors":"Henri Brunner, Masahiro Ikeshita, Takashi Tsuno","doi":"10.1002/ejoc.202400623","DOIUrl":"https://doi.org/10.1002/ejoc.202400623","url":null,"abstract":"In 3/2‐systems, such as the acetate anion H<jats:sub>3</jats:sub>C<jats:sub>α</jats:sub>C′OO<jats:sup>−</jats:sup>, an sp<jats:sup>3</jats:sup> center and an sp<jats:sup>2</jats:sup> center are connected by a covalent bond. The interaction of threefold and twofold symmetry results in the pyramidalization of the sp<jats:sup>2</jats:sup> center during rotation about bond E<jats:sub>sp3</jats:sub>−E<jats:sub>sp2</jats:sub>. Rotation angles <jats:italic>ψ</jats:italic>=0°, ±60°, ±120°, and ±180° account for conformations with a symmetry plane containing the planar sp<jats:sup>2</jats:sup> center C<jats:sub>α</jats:sub>C′OO. However, in all conformations with rotation angles <jats:italic>ψ</jats:italic>≠0°, ±60°, ±120°, and ±180° this symmetry plane is lost and pyramidalization must occur with maxima at rotation angles <jats:italic>ψ</jats:italic>=±30°, ±90°, and ±150°, because the two sides of the sp<jats:sup>2</jats:sup> center C<jats:sub>α</jats:sub>C′OO are different. Inevitably, this leads to a pyramidalization/rotation profile <jats:italic>θ/ψ</jats:italic> with three maxima, three minima, and six zero‐crossings. Thus, myriads of 3/2‐compounds pyramidalize their sp<jats:sup>2</jats:sup> centers each moment to the order of about 2° in a coupled pyramidalization/rotation molecular motion independent of energy.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"11 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142541392","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}
Phase-transfer catalysts (PTCs) are chemical agents that facilitate the transfer of molecules or ions between different reaction phases, thereby accelerating heterogeneous reaction processes. Transition metal catalysts are renowned for their versatility in breaking inert chemical bonds and forming new carbon-carbon bonds. Over the past two decades, integrating metal catalysts with phase-transfer catalysts has emerged as a highly valuable and adaptable strategy in modern organic synthesis. This combined catalytic approach highlights the enhanced synthetic capabilities and demonstrates the benefits of merging these two catalytic systems. This review provides an overview of recent advancements in asymmetric catalysis that utilize the synergy between metal and phase-transfer catalysts, focusing on their role in the rapid and efficient synthesis of complex organic molecules with precise stereochemistry.
{"title":"Advances in Combined Asymmetric Catalysis of Transition Metal/Phase Transfer Catalysts","authors":"Yi-Fan Dong, Si-Ru Wang, Zhi-Yong Han, Xiang Wu","doi":"10.1002/ejoc.202401088","DOIUrl":"https://doi.org/10.1002/ejoc.202401088","url":null,"abstract":"Phase-transfer catalysts (PTCs) are chemical agents that facilitate the transfer of molecules or ions between different reaction phases, thereby accelerating heterogeneous reaction processes. Transition metal catalysts are renowned for their versatility in breaking inert chemical bonds and forming new carbon-carbon bonds. Over the past two decades, integrating metal catalysts with phase-transfer catalysts has emerged as a highly valuable and adaptable strategy in modern organic synthesis. This combined catalytic approach highlights the enhanced synthetic capabilities and demonstrates the benefits of merging these two catalytic systems. This review provides an overview of recent advancements in asymmetric catalysis that utilize the synergy between metal and phase-transfer catalysts, focusing on their role in the rapid and efficient synthesis of complex organic molecules with precise stereochemistry.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"12 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142541910","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}
Axially chiral biaryl aldehydes are precursors for the synthesis of axially chiral compounds and novel chiral catalysts of great interest, which play vital roles in extensive research fields. However, limited strategies exist for the efficient synthesis of axially chiral aldehydes, and the construction of structurally diverse axially chiral aldehydes remains challenging. Herein, a strategy is reported for the synthesis of biaryl axially chiral aldehydes with varying structures from biaryl dialdehydes and aromatic amines in the presence of a chiral phosphoric acid catalyst. This protocol features excellent enantioselectivity, mild conditions, and good functional-group tolerance.
{"title":"Synthesis of Chiral Axially Diaryl Aldehydes by Chiral Phosphoric Acid Catalyzed Desymmetrization Reaction","authors":"Lutong Yuan, Lixin Cui, Yuheng Liu, Wenkai Bao, Qiaohong Zhu, Xiaofei Zeng","doi":"10.1002/ejoc.202401038","DOIUrl":"https://doi.org/10.1002/ejoc.202401038","url":null,"abstract":"Axially chiral biaryl aldehydes are precursors for the synthesis of axially chiral compounds and novel chiral catalysts of great interest, which play vital roles in extensive research fields. However, limited strategies exist for the efficient synthesis of axially chiral aldehydes, and the construction of structurally diverse axially chiral aldehydes remains challenging. Herein, a strategy is reported for the synthesis of biaryl axially chiral aldehydes with varying structures from biaryl dialdehydes and aromatic amines in the presence of a chiral phosphoric acid catalyst. This protocol features excellent enantioselectivity, mild conditions, and good functional-group tolerance.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"212 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142536882","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}
Priyank Kumar Sharma, Akanksha Babbar, Sakshi Sahewal, Soumyajit Das
Cyclopenta-annulated polycyclic aromatic hydrocarbons (CP-PAHs) are of significant interest due to their unique optoelectronic properties and applications in organic electronic devices. Phenanthroacephenanthrylene (PAP) isomers are CP-PAHs that have been rarely investigated, and only the [9,10-e]PAP isomer was explored to date. Herein, we report the syntheses, crystal structure and optoelectronic properties of two PAP isomers, 7-ethoxy[2,1-e]PAP 1 and 9-ethoxy[1,2-e]PAP 2. The structural isomers were synthesized in multi-steps, and structural elucidations were performed using NMR, mass, and single-crystal X-ray diffraction analyses, revealing planar backbone of the isomers. UV-visible absorption and fluorescence spectra of compound 1 were red-shifted than that of 2, suggesting smaller HOMO–LUMO energy gap which is further validated by DFT calculations that suggested the lowering of HOMO–LUMO spacing could be attributed to the greater destabilization of HOMO for 1.
环戊烷化多环芳烃（CP-PAHs）因其独特的光电特性和在有机电子设备中的应用而备受关注。菲并蒽(PAP)异构体是很少被研究的 CP-PAHs，迄今为止只有[9,10-e]PAP 异构体被研究过。在此，我们报告了两种 PAP 异构体--7-乙氧基[2,1-e]PAP 1 和 9-乙氧基[1,2-e]PAP 2 的合成、晶体结构和光电特性。这些结构异构体是通过多个步骤合成的，并利用核磁共振、质量和单晶 X 射线衍射分析进行了结构阐释，揭示了异构体的平面骨架。化合物 1 的紫外可见吸收光谱和荧光光谱都比 2 的红移，表明其 HOMO-LUMO 能隙更小，DFT 计算进一步验证了这一点，即 HOMO-LUMO 间距的降低可能是由于 1 的 HOMO 更加不稳定。
{"title":"Syntheses and Properties of Two Isomeric Phenanthroacephenanthrylene Derivatives","authors":"Priyank Kumar Sharma, Akanksha Babbar, Sakshi Sahewal, Soumyajit Das","doi":"10.1002/ejoc.202400991","DOIUrl":"https://doi.org/10.1002/ejoc.202400991","url":null,"abstract":"Cyclopenta-annulated polycyclic aromatic hydrocarbons (CP-PAHs) are of significant interest due to their unique optoelectronic properties and applications in organic electronic devices. Phenanthroacephenanthrylene (PAP) isomers are CP-PAHs that have been rarely investigated, and only the [9,10-e]PAP isomer was explored to date. Herein, we report the syntheses, crystal structure and optoelectronic properties of two PAP isomers, 7-ethoxy[2,1-e]PAP 1 and 9-ethoxy[1,2-e]PAP 2. The structural isomers were synthesized in multi-steps, and structural elucidations were performed using NMR, mass, and single-crystal X-ray diffraction analyses, revealing planar backbone of the isomers. UV-visible absorption and fluorescence spectra of compound 1 were red-shifted than that of 2, suggesting smaller HOMO–LUMO energy gap which is further validated by DFT calculations that suggested the lowering of HOMO–LUMO spacing could be attributed to the greater destabilization of HOMO for 1.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"16 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142541920","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}
Optically active aziridines represent a pivotal class of rigid three-membered nitrogen-heterocyclic compounds found in natural products, pharmaceuticals, agrochemicals, and functional motifs, which have demonstrated outstanding practicability as therapeutic molecular frameworks, versatile synthetic endpoints, and functional materials in both academic and industrial communities. Recent years have witnessed a broad spectrum of prominent breakthroughs in the field of chiral aziridines due to the aziridine-based rigid and three-dimensional pharmacophores, which have resulted in streamlining the drug discovery process. Over the past few decades, particular attention has been directed towards the strategically efficient, versatile, and practical assembly of optically active aziridines. These synthesis approaches have demonstrated great potential in the context of the construction of pharmaceutical molecules, biologically and pharmacologically relevant natural products, and functional materials. In this review, several synthetic strategies for the assembly of chiral aziridines are summarized, which could be divided into five categories; (1) Introduction; (2) Construction of optically active aziridines via reactions of olefines with nitrene sources; (3) Construction of optically active aziridines via reactions of imines with carbenes; (4) Construction of optically active aziridines via reaction of azirines; (5) Construction of optically active aziridines via intramolecular cyclization of amine derivatives.
{"title":"Synthetic Approaches for the Construction of Chiral Aziridines","authors":"Qing-Hui Liu, Jia-Xuan Liu, Ya-Ping Han, Yong-Min Liang, Li-Zeng Peng","doi":"10.1002/ejoc.202401048","DOIUrl":"https://doi.org/10.1002/ejoc.202401048","url":null,"abstract":"Optically active aziridines represent a pivotal class of rigid three-membered nitrogen-heterocyclic compounds found in natural products, pharmaceuticals, agrochemicals, and functional motifs, which have demonstrated outstanding practicability as therapeutic molecular frameworks, versatile synthetic endpoints, and functional materials in both academic and industrial communities. Recent years have witnessed a broad spectrum of prominent breakthroughs in the field of chiral aziridines due to the aziridine-based rigid and three-dimensional pharmacophores, which have resulted in streamlining the drug discovery process. Over the past few decades, particular attention has been directed towards the strategically efficient, versatile, and practical assembly of optically active aziridines. These synthesis approaches have demonstrated great potential in the context of the construction of pharmaceutical molecules, biologically and pharmacologically relevant natural products, and functional materials. In this review, several synthetic strategies for the assembly of chiral aziridines are summarized, which could be divided into five categories; (1) Introduction; (2) Construction of optically active aziridines via reactions of olefines with nitrene sources; (3) Construction of optically active aziridines via reactions of imines with carbenes; (4) Construction of optically active aziridines via reaction of azirines; (5) Construction of optically active aziridines via intramolecular cyclization of amine derivatives.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"15 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142541913","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}
Mathilde A. C. H. Janssen, Rico Rappard, Tom Dekker, Mitchel Heiming, Marjolijn Beens, Dyon Pieters, Brian H. M. Kuijpers, Jorg C. J. Benningshof, Maikel Wijtmans, Iwan J. P. de Esch, Daniel Blanco-Ania, Floris P. J. T. Rutjes
Cyclobutanes have attracted significant interest in medicinal chemistry because of their unique structure and potential advantages in pharmacological properties. In this study a two-diversification-point library of cyclobutanesulfonamides with either carbamates or triazoles was synthesized through a hyperbaric [2+2] cycloaddition reaction between ethenesulfonyl fluoride and tert-butyl vinyl ether as the key step.
{"title":"High-Pressure-Mediated Fragment Library Synthesis of 1,2-Disubsituted Cyclobutane Derivatives","authors":"Mathilde A. C. H. Janssen, Rico Rappard, Tom Dekker, Mitchel Heiming, Marjolijn Beens, Dyon Pieters, Brian H. M. Kuijpers, Jorg C. J. Benningshof, Maikel Wijtmans, Iwan J. P. de Esch, Daniel Blanco-Ania, Floris P. J. T. Rutjes","doi":"10.1002/ejoc.202400797","DOIUrl":"https://doi.org/10.1002/ejoc.202400797","url":null,"abstract":"Cyclobutanes have attracted significant interest in medicinal chemistry because of their unique structure and potential advantages in pharmacological properties. In this study a two-diversification-point library of cyclobutanesulfonamides with either carbamates or triazoles was synthesized through a hyperbaric [2+2] cycloaddition reaction between ethenesulfonyl fluoride and <i>tert</i>-butyl vinyl ether as the key step.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"31 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142536339","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}
Martin Pošta, Margarita Dmitrieva, Chiara Volpe, Václav Matoušek, Blanka Klepetářová, Petr Beier
Copper(I)-mediated azide-alkyne cycloaddition was coupled with cross-coupling for the synthesis of [6,5,5] ring-fused tricyclic triazoles. Copper(I)-mediated azide-alkyne cycloaddition was investigated on 2-iodoaryl propynes or propynones. With catalytic amount of Cu(I) salts or with N-donor ligands on copper only the products of azide-alkyne cycloadditions were formed. However, with an equimolar amount of copper(I) iodide and triethylamine new [6,5,5] ring-fused tricyclic triazoles were formed by azide-alkyne cycloadditon coupled to a cross-coupling reaction.
{"title":"Synthesis of [6,5,5]Ring-Fused Tricyclic Triazoles by Copper-Promoted Double Cyclization","authors":"Martin Pošta, Margarita Dmitrieva, Chiara Volpe, Václav Matoušek, Blanka Klepetářová, Petr Beier","doi":"10.1002/ejoc.202400736","DOIUrl":"https://doi.org/10.1002/ejoc.202400736","url":null,"abstract":"Copper(I)-mediated azide-alkyne cycloaddition was coupled with cross-coupling for the synthesis of [6,5,5] ring-fused tricyclic triazoles. Copper(I)-mediated azide-alkyne cycloaddition was investigated on 2-iodoaryl propynes or propynones. With catalytic amount of Cu(I) salts or with N-donor ligands on copper only the products of azide-alkyne cycloadditions were formed. However, with an equimolar amount of copper(I) iodide and triethylamine new [6,5,5] ring-fused tricyclic triazoles were formed by azide-alkyne cycloadditon coupled to a cross-coupling reaction.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"15 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142490804","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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