Yufan Yang , Dongyang Jiang , Xuan Li , Juxi Wang , Lu Gao , Wanshu Wang , Zhenlei Song
Conventional transetherification involves activation of the ether C–O bond, enabling either C–O/O–H bond metathesis with alcohols or C–O/C–O metathesis with other ethers. Here, we report an alternative approach based on an unusual C–O/C–Br bond metathesis. Silver triflate (AgOTf) promotes the transetherification of p-methoxybenzyl ethers (PMB–OR2) with allyl or benzyl bromides (R1–Br), selectively affording unsymmetrical ethers (R1–O–R2). The reaction tolerates a wide range of functional groups that are incompatible with the strong bases required for Williamson ether synthesis. Furthermore, the method enables a three-component process involving R1–Br, R2–Br, and PMBOH, where PMBOH acts as an “oxygen linker” through a sequential etherification/transetherification process. Mechanistic studies indicate a cationic pathway proceeding via a trialkyl oxonium intermediate.
传统的酯交换反应包括激活乙醚的C-O键，使C-O/O-H键与醇或C-O/C-O与其他醚的转化成为可能。在这里，我们报告了一种基于不寻常的C-O/C-Br键复合的替代方法。三酸银（AgOTf）促进对甲氧基苄基醚（PMB-OR2）与烯丙基溴或苄基溴（r1 -Br）的酯交换反应，选择性地产生不对称醚（r1 - o - r2）。该反应可耐受多种与威廉姆森醚合成所需的强碱不相容的官能团。此外，该方法实现了涉及R¹-Br， R²-Br和PMBOH的三组分过程，其中PMBOH通过顺序醚化/醚化过程作为“氧连接剂”。机理研究表明阳离子途径是通过三烷基氧鎓中间体进行的。
{"title":"AgOTf-promoted transetherification of p-methoxybenzyl ethers with allyl and benzyl bromides","authors":"Yufan Yang , Dongyang Jiang , Xuan Li , Juxi Wang , Lu Gao , Wanshu Wang , Zhenlei Song","doi":"10.1039/d5qo00945f","DOIUrl":"10.1039/d5qo00945f","url":null,"abstract":"<div><div>Conventional transetherification involves activation of the ether C–O bond, enabling either C–O/O–H bond metathesis with alcohols or C–O/C–O metathesis with other ethers. Here, we report an alternative approach based on an unusual C–O/C–Br bond metathesis. Silver triflate (AgOTf) promotes the transetherification of <em>p</em>-methoxybenzyl ethers (PMB–OR<sup>2</sup>) with allyl or benzyl bromides (R<sup>1</sup>–Br), selectively affording unsymmetrical ethers (R<sup>1</sup>–O–R<sup>2</sup>). The reaction tolerates a wide range of functional groups that are incompatible with the strong bases required for Williamson ether synthesis. Furthermore, the method enables a three-component process involving R<sup>1</sup>–Br, R<sup>2</sup>–Br, and PMBOH, where PMBOH acts as an “oxygen linker” through a sequential etherification/transetherification process. Mechanistic studies indicate a cationic pathway proceeding <em>via</em> a trialkyl oxonium intermediate.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 24","pages":"Pages 6820-6825"},"PeriodicalIF":0.0,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145017826","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Bei Wan , Ce Liu , Haoyuan Xiong , Yi Deng , Zhonghua Gu , Shaoyu Mai , Feng Qiu , Qingfeng Du
We report herein the first Suzuki-type [3 + 2] cyclization of cyclic 1,3-dicarbonyls with readily available 2-aminoarylboronic esters to synthesize carbazolones. With environmentally benign EtOH/H2O as solvent, a series of structurally and electronically diverse carbazolones can be readily obtained in a modular manner. This approach is mild, operationally simple, high yielding, scalable, and highly tolerant to moisture and air. Notably, it also exhibits excellent compatibility with various heterocyclic 1,3-dicarbonyls. The utility of this method has further been demonstrated by the late-stage functionalization of complex structures (e.g. styrylpyrone and simvastatin) and formal total synthesis of isocryptolepine.
{"title":"Rh-catalyzed [3 + 2] cyclization of (hetero)cyclic 1,3-dicarbonyls with 2-aminoarylboronic esters to access carbazolones","authors":"Bei Wan , Ce Liu , Haoyuan Xiong , Yi Deng , Zhonghua Gu , Shaoyu Mai , Feng Qiu , Qingfeng Du","doi":"10.1039/d5qo01079a","DOIUrl":"10.1039/d5qo01079a","url":null,"abstract":"<div><div>We report herein the first Suzuki-type [3 + 2] cyclization of cyclic 1,3-dicarbonyls with readily available 2-aminoarylboronic esters to synthesize carbazolones. With environmentally benign EtOH/H<sub>2</sub>O as solvent, a series of structurally and electronically diverse carbazolones can be readily obtained in a modular manner. This approach is mild, operationally simple, high yielding, scalable, and highly tolerant to moisture and air. Notably, it also exhibits excellent compatibility with various heterocyclic 1,3-dicarbonyls. The utility of this method has further been demonstrated by the late-stage functionalization of complex structures (<em>e.g.</em> styrylpyrone and simvastatin) and formal total synthesis of isocryptolepine.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 24","pages":"Pages 7049-7054"},"PeriodicalIF":0.0,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145127979","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yi-Yun Zhu , Wen-Hao Li , Yan-Qi Fan , Hao-Chen Lu , Donghui Wei , Xuenian Chen
Solid-state luminescence is often hindered by aggregation-caused quenching (ACQ), prompting the search for efficient aggregation-induced emission (AIE) materials. Tetraphenylethylene (TPE), a star molecule in AIE research, has been widely used to study the restricted intramolecular motion (RIM) mechanism through structural modifications. Breaking from traditional peripheral modification, we engineer the TPE core by inserting an alkynyl linker between the triphenylethylene (TriPE) core and planar chromophores (), where the alkynyl bond length and spatial orientation dictate molecular conformations, intermolecular interactions, and crystal packing, as well as the torsional oscillation along the rotation axis. The exhibits J-aggregation-enhanced emission, with quantum yields of 69.9% in the solid state and 88.4% in the crystal. This central modification strategy opens new avenues for designing advanced AIE materials.
{"title":"Alkyne-inserted tetraphenylethylene derivatives: enhanced aggregation-induced emission via intramolecular and intermolecular interactions","authors":"Yi-Yun Zhu , Wen-Hao Li , Yan-Qi Fan , Hao-Chen Lu , Donghui Wei , Xuenian Chen","doi":"10.1039/d5qo01158b","DOIUrl":"10.1039/d5qo01158b","url":null,"abstract":"<div><div>Solid-state luminescence is often hindered by aggregation-caused quenching (ACQ), prompting the search for efficient aggregation-induced emission (AIE) materials. Tetraphenylethylene (TPE), a star molecule in AIE research, has been widely used to study the restricted intramolecular motion (RIM) mechanism through structural modifications. Breaking from traditional peripheral modification, we engineer the TPE core by inserting an alkynyl linker between the triphenylethylene (TriPE) core and planar chromophores (), where the alkynyl bond length and spatial orientation dictate molecular conformations, intermolecular interactions, and crystal packing, as well as the torsional oscillation along the rotation axis. The exhibits J-aggregation-enhanced emission, with quantum yields of 69.9% in the solid state and 88.4% in the crystal. This central modification strategy opens new avenues for designing advanced AIE materials.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 24","pages":"Pages 6894-6901"},"PeriodicalIF":0.0,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145059783","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sulfur-containing compounds have broad application prospects in chemical biology and medicinal chemistry. Herein we have reported Cu-catalyzed sulfilimine synthesis via arylation, alkylation and alkenylation of sulfenamides using readily accessible thianthrenium salts. The protocol allows a universal modular late-stage sulfilimination of highly functionalized molecules, and the sulfilimine motif can be easily transformed into sulfoximine and sulfondiimine derivatives. Mechanistic studies suggest that the bifunctional Cu catalyst plays an important role in the reaction, facilitating both the EDA association and the C–S coupling.
{"title":"Synthesis of sulfilimines via electron donor–acceptor complexes","authors":"Ke Wu , Junliang Zhang , Junfeng Yang","doi":"10.1039/d5qo01017a","DOIUrl":"10.1039/d5qo01017a","url":null,"abstract":"<div><div>Sulfur-containing compounds have broad application prospects in chemical biology and medicinal chemistry. Herein we have reported Cu-catalyzed sulfilimine synthesis <em>via</em> arylation, alkylation and alkenylation of sulfenamides using readily accessible thianthrenium salts. The protocol allows a universal modular late-stage sulfilimination of highly functionalized molecules, and the sulfilimine motif can be easily transformed into sulfoximine and sulfondiimine derivatives. Mechanistic studies suggest that the bifunctional Cu catalyst plays an important role in the reaction, facilitating both the EDA association and the C–S coupling.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 24","pages":"Pages 7118-7126"},"PeriodicalIF":0.0,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189231","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jianyue Bi , Zhenxing Zhang , Yuanhao He , Huajian Li , Xinming Yan , Fen Zhao , Fang Dai , Baomin Fan
Herein, we report the gold-catalyzed spirocyclization of activated alkynes with organoiodides through ligand-enabled gold redox catalysis. The reaction proceeds smoothly under mild conditions and without the need for an external oxidant, affording a series of 3-arylated, 3-alkenylated, and 3-alkynylated spiro[4.5]trienones in good to excellent yields. This transformation exhibits a broad substrate scope, good functional group tolerance, and compatibility with heteroaromatic systems. The (P,N) ligand MeDalPhos-facilitated gold-catalyzed process provides a new strategy for the synthesis of 3-substituted spiro[4.5]trienones. Furthermore, mechanistic investigations, including NMR and mass spectrometric studies, strongly support the proposed reaction mechanism.
{"title":"Gold-catalyzed spirocyclization of activated alkynes with organoiodides: access to 3-arylated, 3-alkenylated, and 3-alkynylated spiro[4.5]trienones","authors":"Jianyue Bi , Zhenxing Zhang , Yuanhao He , Huajian Li , Xinming Yan , Fen Zhao , Fang Dai , Baomin Fan","doi":"10.1039/d5qo01065a","DOIUrl":"10.1039/d5qo01065a","url":null,"abstract":"<div><div>Herein, we report the gold-catalyzed spirocyclization of activated alkynes with organoiodides through ligand-enabled gold redox catalysis. The reaction proceeds smoothly under mild conditions and without the need for an external oxidant, affording a series of 3-arylated, 3-alkenylated, and 3-alkynylated spiro[4.5]trienones in good to excellent yields. This transformation exhibits a broad substrate scope, good functional group tolerance, and compatibility with heteroaromatic systems. The (P,N) ligand MeDalPhos-facilitated gold-catalyzed process provides a new strategy for the synthesis of 3-substituted spiro[4.5]trienones. Furthermore, mechanistic investigations, including NMR and mass spectrometric studies, strongly support the proposed reaction mechanism.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 24","pages":"Pages 7010-7018"},"PeriodicalIF":0.0,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145103780","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A novel protocol for the arylation of arylazo sulfones with organomagnesiums for accessing non-symmetric ortho-functionalized azoarenes has been successfully developed. Bench-stable substituted arylazo sulfones, which serve as masked electrophilic diazo sources, have been effectively arylated, achieving good to excellent isolated yields. This method demonstrates broad tolerance towards a wide variety of substituents. Furthermore, the mechanism and the regioselectivity of the addition have been investigated using DFT calculations. The observed regioselectivity would arise from a combination of steric and electronic effects, as well as the presence or absence of a strongly coordinating substituent at the ortho position of the starting material.
{"title":"Synthesis of non-symmetric ortho-functionalized azoarenes through arylation of arylazo sulfones","authors":"Rayhane Hammami , Victor Flon , Morgane Sanselme , Julien Legros , Isabelle Chataigner , Laëtitia Chausset-Boissarie","doi":"10.1039/d5qo00932d","DOIUrl":"10.1039/d5qo00932d","url":null,"abstract":"<div><div>A novel protocol for the arylation of arylazo sulfones with organomagnesiums for accessing non-symmetric <em>ortho</em>-functionalized azoarenes has been successfully developed. Bench-stable substituted arylazo sulfones, which serve as masked electrophilic diazo sources, have been effectively arylated, achieving good to excellent isolated yields. This method demonstrates broad tolerance towards a wide variety of substituents. Furthermore, the mechanism and the regioselectivity of the addition have been investigated using DFT calculations. The observed regioselectivity would arise from a combination of steric and electronic effects, as well as the presence or absence of a strongly coordinating substituent at the <em>ortho</em> position of the starting material.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 24","pages":"Pages 6953-6960"},"PeriodicalIF":0.0,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145077921","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The integration of γ-keto sulfones, despite being medicinally relevant building blocks, with the bioactive diarylmethane motif remains elusive. On the other hand, the fixation of SO2 into organic molecules for accessing value-added products is gaining wide attention in organic synthesis. Herein, we disclose the 1,6-hydrosulfonylation of p-quinone methides via the strain-release driven ring-scission of strained 3°-cyclopropanols in the presence of a SO2-surrogate like K2S2O5 and a Brønsted acid under visible-light photoredox catalysis to access a library of γ-keto alkylsulfonylated diarylmethanes in moderate to good yields. Also, the 1,6-hydrosulfonylation of p-quinone methides has been developed via aromaticity-driven bond-scission in pro-aromatics like 4-alkyl-1,4-DHPs in the presence of K2S2O5 and a Brønsted acid under visible-light photoredox catalysis to access a library of alkylsulfonylated diarylmethanes. The efficiency of the developed reactions has been established through broad substrate-scope studies, and the mechanistic probing studies have been complemented with DFT calculations to support the proposed mechanisms. In addition, antiproliferative studies revealed oral cancer activity for some of the synthesized sulfonylated diarylmethane derivatives.
{"title":"1,6-Hydrosulfonylation of p-quinone methides enabled via strain-release-/aromaticity-driven alkyl radical generation and SO2-capture: synthesis and antiproliferative studies of sulfonylated diarylmethanes","authors":"Dipun Kumar Penthi , Tonish Kumar Sahu , Rahimuddin Khan , Shanti Gopal Patra , Tabrez Khan","doi":"10.1039/d5qo00981b","DOIUrl":"10.1039/d5qo00981b","url":null,"abstract":"<div><div>The integration of γ-keto sulfones, despite being medicinally relevant building blocks, with the bioactive diarylmethane motif remains elusive. On the other hand, the fixation of SO<sub>2</sub> into organic molecules for accessing value-added products is gaining wide attention in organic synthesis. Herein, we disclose the 1,6-hydrosulfonylation of <em>p</em>-quinone methides <em>via</em> the strain-release driven ring-scission of strained 3°-cyclopropanols in the presence of a SO<sub>2</sub>-surrogate like K<sub>2</sub>S<sub>2</sub>O<sub>5</sub> and a Brønsted acid under visible-light photoredox catalysis to access a library of γ-keto alkylsulfonylated diarylmethanes in moderate to good yields. Also, the 1,6-hydrosulfonylation of <em>p</em>-quinone methides has been developed <em>via</em> aromaticity-driven bond-scission in pro-aromatics like 4-alkyl-1,4-DHPs in the presence of K<sub>2</sub>S<sub>2</sub>O<sub>5</sub> and a Brønsted acid under visible-light photoredox catalysis to access a library of alkylsulfonylated diarylmethanes. The efficiency of the developed reactions has been established through broad substrate-scope studies, and the mechanistic probing studies have been complemented with DFT calculations to support the proposed mechanisms. In addition, antiproliferative studies revealed oral cancer activity for some of the synthesized sulfonylated diarylmethane derivatives.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 24","pages":"Pages 6922-6935"},"PeriodicalIF":0.0,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145025278","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A streamlined and efficient synthetic strategy has been established for the construction of indolo[2,3-b]quinolines, utilizing C3-alkylated indole as the starting material and mediated by DMSO and HCl. This methodology enables the direct annulation of the quinoline ring onto a pre-functionalized indole core with high functional group compatibility. The reaction proceeds smoothly across a diverse range of substrates, delivering the desired products in consistently high yields. Its operational simplicity, scalability, and broad substrate scope highlight its practical utility, particularly for large-scale synthesis. Notably, this approach provides a valuable platform for the synthesis of complex natural products featuring the indolo[2,3-b]quinoline framework. Indolo[2,3-b]quinolines show strong blue to blue-green fluorescence with large Stokes shifts due to excited-state proton transfer. Substituents on the pyrrolic nitrogen and aromatic core significantly affect absorption and emission by altering hydrogen bonding and photobasicity. Electron-donating groups at the 5-position increase fluorescence lifetime and quantum yield.
{"title":"Facile access to indolo[2,3-b]quinoline alkaloids via DMSO-mediated cascade cyclization: unveiling their photophysical potential","authors":"Gokulprasanth Nataraj , Ranjithkumar Chandran , Muniappan Kalipriyadharshini , Diksha Bansal , Easwaramoorthi Shanmugam , Mrinal Kanti Das , Saikat Chaudhuri","doi":"10.1039/d5qo01193k","DOIUrl":"10.1039/d5qo01193k","url":null,"abstract":"<div><div>A streamlined and efficient synthetic strategy has been established for the construction of indolo[2,3-<em>b</em>]quinolines, utilizing C3-alkylated indole as the starting material and mediated by DMSO and HCl. This methodology enables the direct annulation of the quinoline ring onto a pre-functionalized indole core with high functional group compatibility. The reaction proceeds smoothly across a diverse range of substrates, delivering the desired products in consistently high yields. Its operational simplicity, scalability, and broad substrate scope highlight its practical utility, particularly for large-scale synthesis. Notably, this approach provides a valuable platform for the synthesis of complex natural products featuring the indolo[2,3-<em>b</em>]quinoline framework. Indolo[2,3-<em>b</em>]quinolines show strong blue to blue-green fluorescence with large Stokes shifts due to excited-state proton transfer. Substituents on the pyrrolic nitrogen and aromatic core significantly affect absorption and emission by altering hydrogen bonding and photobasicity. Electron-donating groups at the 5-position increase fluorescence lifetime and quantum yield.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 24","pages":"Pages 7081-7090"},"PeriodicalIF":0.0,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183374","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Aryl iodides are indispensable intermediates in organic synthesis, yet direct C–H iodination of electronically diverse arenes under mild conditions remains challenging. Herein, we disclose a general and operationally simple C–H iodination protocol leveraging the I2/Selectfluor system, with Sc(OTf)3–HFIP activation enabling efficient iodination of electron-deficient arenes. This method exhibits broad substrate scope, accommodating diverse functional groups, heteroarenes, and complex drug-like molecules. Control experiments support a mechanism wherein activation of I2 by Selectfluor generates a highly electrophilic iodonium species for iodination. Moreover, a related LiBr/Selectfluor system enables efficient C–H bromination of (hetero)arenes under similarly mild conditions.
{"title":"Selectfluor-promoted electrophilic aromatic halogenation: a general strategy for iodination and bromination via oxidative halide activation","authors":"Fan Wu , Yuying Weng , Xubing Hu , Feng Ni","doi":"10.1039/d5qo01114k","DOIUrl":"10.1039/d5qo01114k","url":null,"abstract":"<div><div>Aryl iodides are indispensable intermediates in organic synthesis, yet direct C–H iodination of electronically diverse arenes under mild conditions remains challenging. Herein, we disclose a general and operationally simple C–H iodination protocol leveraging the I<sub>2</sub>/Selectfluor system, with Sc(OTf)<sub>3</sub>–HFIP activation enabling efficient iodination of electron-deficient arenes. This method exhibits broad substrate scope, accommodating diverse functional groups, heteroarenes, and complex drug-like molecules. Control experiments support a mechanism wherein activation of I<sub>2</sub> by Selectfluor generates a highly electrophilic iodonium species for iodination. Moreover, a related LiBr/Selectfluor system enables efficient C–H bromination of (hetero)arenes under similarly mild conditions.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 24","pages":"Pages 7075-7080"},"PeriodicalIF":0.0,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183373","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Bendu Pan , Yunru Wu , Liwei Zhao , Rihui Cao , Liqin Qiu
Herein, we report a novel metal-free cascade SNAr reaction/allylic amination strategy toward pyrimidinamine derivatives promoted by cost-effective triethylamine, enabling the efficient synthesis of a wide range of 2-chlorotetrahydropteridines in moderate to good yields under an air atmosphere. This operationally simple protocol demonstrates notable advantages including one-pot synthesis and utilization of environmentally benign solvents. The obtained 2-chlorotetrahydropteridines serve as versatile synthons for constructing diverse 2-substituted tetrahydropteridine derivatives through conventional palladium-catalyzed Suzuki-coupling and Buchwald–Hartwig amination reactions using as the N-heterocyclic carbene–palladium catalyst. Systematic mechanistic investigations, including successful isolation and monitoring of key intermediates, provide a deeper insight into the reaction pathway. The methodology's sustainability is further demonstrated through solvent-free optimization, feasibility for gram-scale production, and synthetic application of the resulting products. This green synthetic approach significantly reduces environmental impact by eliminating the need for an inert atmosphere, establishing a robust platform for the sustainable synthesis of tetrahydropteridines.
{"title":"Metal-free cascade SNAr reaction/allylic amination enabled by triethylamine: a green chemistry approach to access tetrahydropteridines","authors":"Bendu Pan , Yunru Wu , Liwei Zhao , Rihui Cao , Liqin Qiu","doi":"10.1039/d5qo01211b","DOIUrl":"10.1039/d5qo01211b","url":null,"abstract":"<div><div>Herein, we report a novel metal-free cascade S<sub>N</sub>Ar reaction/allylic amination strategy toward pyrimidinamine derivatives promoted by cost-effective triethylamine, enabling the efficient synthesis of a wide range of 2-chlorotetrahydropteridines in moderate to good yields under an air atmosphere. This operationally simple protocol demonstrates notable advantages including one-pot synthesis and utilization of environmentally benign solvents. The obtained 2-chlorotetrahydropteridines serve as versatile synthons for constructing diverse 2-substituted tetrahydropteridine derivatives through conventional palladium-catalyzed Suzuki-coupling and Buchwald–Hartwig amination reactions using as the N-heterocyclic carbene–palladium catalyst. Systematic mechanistic investigations, including successful isolation and monitoring of key intermediates, provide a deeper insight into the reaction pathway. The methodology's sustainability is further demonstrated through solvent-free optimization, feasibility for gram-scale production, and synthetic application of the resulting products. This green synthetic approach significantly reduces environmental impact by eliminating the need for an inert atmosphere, establishing a robust platform for the sustainable synthesis of tetrahydropteridines.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 24","pages":"Pages 7127-7135"},"PeriodicalIF":0.0,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203645","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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