Pub Date : 2025-10-13Epub Date: 2025-09-15DOI: 10.1039/d5qo01195g
Pedro Pauletto , Davi F. Back , Cristina Wayne Nogueira , Gilson Zeni
This manuscript reports a selective diorganyl diselenide/iron(iii)-promoted strategy for the synthesis of selenium-containing heterocycles, specifically naphtho[2,1-b]selenophene derivatives, via cascade cyclization reactions. Using 1,3-diynylpropargyl alcohols as key substrates and diorganyl diselenides as selenium sources, the optimized conditions involve iron(iii) chloride and dibutyl diselenide in dichloromethane under an inert atmosphere at room temperature, followed by the addition of the substrate and stirring for 12 hours. A series of 25 novel derivatives was synthesized in good yields, demonstrating the scope and versatility of the protocol, which was also extended to include diorganyl disulfides. However, the optimized conditions did not work for diorganyl ditellurides, even when some reaction parameters were changed. The reaction mechanism insights are discussed, and the synthetic utility of the resulting heterocycles as intermediates in further transformations is showcased. This cascade process enables the formation of four new bonds (carbon–carbon, carbon–selenium, selenium–carbon, and carbon–selenium) in a single reaction step.
{"title":"Regioselective formation of naphtho[2,1-b]selenophenes via cascade cyclization of 1,3-diynylpropargyl alcohols promoted by iron(iii) chloride and diorganyl diselenides","authors":"Pedro Pauletto , Davi F. Back , Cristina Wayne Nogueira , Gilson Zeni","doi":"10.1039/d5qo01195g","DOIUrl":"10.1039/d5qo01195g","url":null,"abstract":"<div><div>This manuscript reports a selective diorganyl diselenide/iron(<span>iii</span>)-promoted strategy for the synthesis of selenium-containing heterocycles, specifically naphtho[2,1-<em>b</em>]selenophene derivatives, <em>via</em> cascade cyclization reactions. Using 1,3-diynylpropargyl alcohols as key substrates and diorganyl diselenides as selenium sources, the optimized conditions involve iron(<span>iii</span>) chloride and dibutyl diselenide in dichloromethane under an inert atmosphere at room temperature, followed by the addition of the substrate and stirring for 12 hours. A series of 25 novel derivatives was synthesized in good yields, demonstrating the scope and versatility of the protocol, which was also extended to include diorganyl disulfides. However, the optimized conditions did not work for diorganyl ditellurides, even when some reaction parameters were changed. The reaction mechanism insights are discussed, and the synthetic utility of the resulting heterocycles as intermediates in further transformations is showcased. This cascade process enables the formation of four new bonds (carbon–carbon, carbon–selenium, selenium–carbon, and carbon–selenium) in a single reaction step.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 24","pages":"Pages 6826-6833"},"PeriodicalIF":0.0,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145059782","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}
Pub Date : 2025-10-13Epub Date: 2025-09-15DOI: 10.1039/d5qo01139f
Hui-Qi Mo , Cheng Hou
Pyrazole-based transition metal complexes have attracted increasing attention in borrowing hydrogen (BH) reactions, particularly when employing the metal–ligand cooperation (MLC) strategy to achieve high activity and selectivity. However, a systematic understanding of their mechanistic selectivity and the factors governing catalytic performance remains lacking. Herein, the BH reaction of alcohols catalyzed by such complexes was investigated using density functional theory (DFT) calculations in combination with machine learning (ML) methods. Three possible pathways—N2-site-assisted, O-site-assisted, and N1-site-assisted—were proposed, among which the N2-site-assisted route was identified as the most favorable. Both the dehydrogenation and hydrogenation steps proceed via an outer-sphere concerted transfer mechanism. Distortion/interaction analysis revealed that the ligand-assisted distortion energy plays a decisive role in determining the activation barrier. Furthermore, an ML model with high predictive accuracy (R2 = 0.9570) was established to correlate catalytic performance with electronic and steric descriptors. Feature importance analysis identified the HOMO energy level, dipole moment, and molecular volume as key factors, reflecting the roles of electron-donating ability, transition-state polarization, and steric effects, respectively. This study not only deepens the mechanistic understanding of MLC-enabled BH reactions catalyzed by pyrazole-based transition metal complexes but also provides a predictive framework for the rational design of efficient and tunable catalysts.
{"title":"Mechanistic and machine learning insights into borrowing hydrogen reactions catalyzed by transition metal complexes with N-heterocyclic ligands","authors":"Hui-Qi Mo , Cheng Hou","doi":"10.1039/d5qo01139f","DOIUrl":"10.1039/d5qo01139f","url":null,"abstract":"<div><div>Pyrazole-based transition metal complexes have attracted increasing attention in borrowing hydrogen (BH) reactions, particularly when employing the metal–ligand cooperation (MLC) strategy to achieve high activity and selectivity. However, a systematic understanding of their mechanistic selectivity and the factors governing catalytic performance remains lacking. Herein, the BH reaction of alcohols catalyzed by such complexes was investigated using density functional theory (DFT) calculations in combination with machine learning (ML) methods. Three possible pathways—N2-site-assisted, O-site-assisted, and N1-site-assisted—were proposed, among which the N2-site-assisted route was identified as the most favorable. Both the dehydrogenation and hydrogenation steps proceed <em>via</em> an outer-sphere concerted transfer mechanism. Distortion/interaction analysis revealed that the ligand-assisted distortion energy plays a decisive role in determining the activation barrier. Furthermore, an ML model with high predictive accuracy (<em>R</em><sup>2</sup> = 0.9570) was established to correlate catalytic performance with electronic and steric descriptors. Feature importance analysis identified the HOMO energy level, dipole moment, and molecular volume as key factors, reflecting the roles of electron-donating ability, transition-state polarization, and steric effects, respectively. This study not only deepens the mechanistic understanding of MLC-enabled BH reactions catalyzed by pyrazole-based transition metal complexes but also provides a predictive framework for the rational design of efficient and tunable catalysts.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 24","pages":"Pages 6902-6914"},"PeriodicalIF":0.0,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145059784","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}
Pub Date : 2025-10-13Epub Date: 2025-09-11DOI: 10.1039/d5qo01138h
Yuhang Luo , Xiangxiang Li , Xinjie Zhao , Baomin Yang , Yubo Wei , Guiping Qin
A copper-catalyzed cyanoalkyl-alkynylation of gem-disubstituted alkenes for the construction of alkynyl all-carbon quaternary centers is reported herein. This protocol enables the efficient synthesis of various cyano compounds with an alkynyl all-carbon quaternary center in good yields and overcomes the challenges posed by large steric hindrance and unstable alkylmetal species by using pyridine as a directing group. Preliminary mechanism studies indicated that a radical pathway might be potentially involved in this reaction.
{"title":"Cu-catalyzed cyanoalkyl-alkynylation of gem-disubstituted alkenes to construct all-carbon quaternary center compounds","authors":"Yuhang Luo , Xiangxiang Li , Xinjie Zhao , Baomin Yang , Yubo Wei , Guiping Qin","doi":"10.1039/d5qo01138h","DOIUrl":"10.1039/d5qo01138h","url":null,"abstract":"<div><div>A copper-catalyzed cyanoalkyl-alkynylation of <em>gem</em>-disubstituted alkenes for the construction of alkynyl all-carbon quaternary centers is reported herein. This protocol enables the efficient synthesis of various cyano compounds with an alkynyl all-carbon quaternary center in good yields and overcomes the challenges posed by large steric hindrance and unstable alkylmetal species by using pyridine as a directing group. Preliminary mechanism studies indicated that a radical pathway might be potentially involved in this reaction.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 24","pages":"Pages 6936-6943"},"PeriodicalIF":0.0,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145035571","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}
Pub Date : 2025-10-13Epub Date: 2025-09-30DOI: 10.1039/d5qo01173f
Ping Wu , Guan-Sheng Jiao , Cheng-Pan Zhang
A useful method for the preparation of aryl ketones from arylsulfonium salts and nitriles via nickel catalysis is described. The reaction proceeds smoothly under mild conditions and exhibits obvious advantages, such as high efficiency, good functional group tolerance, excellent chemoselectivity, and the ability to acylate complex drug molecules. This protocol provides a practical synthetic route for synthesizing a wide variety of aryl ketones and enables the selective coupling of arylsulfonium salts while retaining other functionalizable handles. Additionally, the easily available deuterated acetonitrile can be used as the nitrile source, which allows for deuteration with good yields and deuterium content up to 99%, permitting effective deuterium labeling of various complex drug molecules.
{"title":"Nickel-catalyzed synthesis of aryl ketones from arylsulfonium salts and nitriles","authors":"Ping Wu , Guan-Sheng Jiao , Cheng-Pan Zhang","doi":"10.1039/d5qo01173f","DOIUrl":"10.1039/d5qo01173f","url":null,"abstract":"<div><div>A useful method for the preparation of aryl ketones from arylsulfonium salts and nitriles <em>via</em> nickel catalysis is described. The reaction proceeds smoothly under mild conditions and exhibits obvious advantages, such as high efficiency, good functional group tolerance, excellent chemoselectivity, and the ability to acylate complex drug molecules. This protocol provides a practical synthetic route for synthesizing a wide variety of aryl ketones and enables the selective coupling of arylsulfonium salts while retaining other functionalizable handles. Additionally, the easily available deuterated acetonitrile can be used as the nitrile source, which allows for deuteration with good yields and deuterium content up to 99%, permitting effective deuterium labeling of various complex drug molecules.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 24","pages":"Pages 7097-7106"},"PeriodicalIF":0.0,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189232","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}
Pub Date : 2025-10-13Epub Date: 2025-09-17DOI: 10.1039/d5qo01119a
Mattis Damrath , Boris J. Nachtsheim
The ring opening of aziridines to produce various N-heterocycles traditionally requires strong Lewis acids or transition metal catalysts, with non-covalent organocatalytic approaches remaining largely unexplored. Herein, we demonstrate that N-heterocyclic iodonium salts can effectively catalyze [3 + 2] cycloadditions of aziridines through a monodentate halogen bond (XB) activation. Using 1–5 mol% of the iodolium catalyst, a wide range of aziridines undergo an efficient cycloaddition with a variety of dipolarophiles (carbonyls, alkynes, and alkenes) to furnish oxazolidines, pyrrolines, and pyrrolidines. DFT calculations revealed a previously underexplored N-activation mode, with detailed non-covalent interaction analysis showing that the N-heterocyclic iodonium salt's exceptional performance stems from combined I–N and I–π interactions.
{"title":"Monodentate halogen bond activation of aziridines in formal [3 + 2] cycloadditions","authors":"Mattis Damrath , Boris J. Nachtsheim","doi":"10.1039/d5qo01119a","DOIUrl":"10.1039/d5qo01119a","url":null,"abstract":"<div><div>The ring opening of aziridines to produce various N-heterocycles traditionally requires strong Lewis acids or transition metal catalysts, with non-covalent organocatalytic approaches remaining largely unexplored. Herein, we demonstrate that N-heterocyclic iodonium salts can effectively catalyze [3 + 2] cycloadditions of aziridines through a monodentate halogen bond (XB) activation. Using 1–5 mol% of the iodolium catalyst, a wide range of aziridines undergo an efficient cycloaddition with a variety of dipolarophiles (carbonyls, alkynes, and alkenes) to furnish oxazolidines, pyrrolines, and pyrrolidines. DFT calculations revealed a previously underexplored <em>N</em>-activation mode, with detailed non-covalent interaction analysis showing that the N-heterocyclic iodonium salt's exceptional performance stems from combined I–N and I–π interactions.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 24","pages":"Pages 6841-6851"},"PeriodicalIF":0.0,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145077871","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}
In previous reports, the cross-couplings of diaryl disulfides with aryl halides in the presence of transition metal catalysts (e.g., Ni and Cu) and metal mediators (e.g., Mg and Zn) usually led to the corresponding aryl sulfides via old S–S bond cleavage and new C–S bond formation. In the present study, we found that the reductive cross-couplings of diaryl disulfides with aryl bromides proceeded via unusual C–S bond cleavage in the presence of a nickel catalyst, magnesium, and lithium chloride in THF at room temperature, leading to a variety of biaryls in modest to good yields. In addition, the reaction could be scaled up with ease. Mechanistic studies showed that the reaction possibly proceeds via the in situ production of an arylmagnesium compound as a reaction intermediate via LiCl-facilitated Mg insertion into aryl bromide. Most importantly, the combinatory use of the Ni(ii) catalyst and Mg mediator is key to the unusual cleavage of the C–S bond in diaryl disulfide to form the corresponding arylnickel(ii) species, which serves as another important intermediate in the present desulfurative cross-coupling reaction.
{"title":"Ni-catalyzed reductive cross-couplings of diaryl disulfides with aryl bromides for biaryl synthesis through C–S bond cleavage†","authors":"Xuan-Qi Zhang , Cai-Yu He , Shuang-Feng Song , Xue-Qiang Chu , Hao Xu , Xiaocong Zhou , Weidong Rao , Zhi-Liang Shen","doi":"10.1039/d5qo00546a","DOIUrl":"10.1039/d5qo00546a","url":null,"abstract":"<div><div>In previous reports, the cross-couplings of diaryl disulfides with aryl halides in the presence of transition metal catalysts (<em>e.g.</em>, Ni and Cu) and metal mediators (<em>e.g.</em>, Mg and Zn) usually led to the corresponding aryl sulfides <em>via</em> old S–S bond cleavage and new C–S bond formation. In the present study, we found that the reductive cross-couplings of diaryl disulfides with aryl bromides proceeded <em>via</em> unusual C–S bond cleavage in the presence of a nickel catalyst, magnesium, and lithium chloride in THF at room temperature, leading to a variety of biaryls in modest to good yields. In addition, the reaction could be scaled up with ease. Mechanistic studies showed that the reaction possibly proceeds <em>via</em> the <em>in situ</em> production of an arylmagnesium compound as a reaction intermediate <em>via</em> LiCl-facilitated Mg insertion into aryl bromide. Most importantly, the combinatory use of the Ni(<span>ii</span>) catalyst and Mg mediator is key to the unusual cleavage of the C–S bond in diaryl disulfide to form the corresponding arylnickel(<span>ii</span>) species, which serves as another important intermediate in the present desulfurative cross-coupling reaction.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5459-5466"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144211687","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}
Pub Date : 2025-09-05Epub Date: 2025-06-02DOI: 10.1039/d5qo00626k
Sakshi Singh , Samir Kumar Mondal , Shantanu Pal
Chemodivergent approaches strive to enable achieving regioselective and site-divergent transformations of multiple products from identical, readily accessible starting materials by changing the reaction parameters, but are challenging due to the complexity of precisely controlling the chemodiversity. Herein, we report a novel FeCl3-catalyzed one-pot strategy involving switching the temperature to enable the selective synthesis of 5-methyl-7-phenyldibenzo[b,h][1,6] naphthy-ridin-6(5H)-one or 3-phenyl-1H-indole from o-vinylaniline and N-substituted isatin. Notably, the reaction exhibits temperature-controlled chemodivergence, selectively yielding either intramolecular or intermolecular products. This approach demonstrates a wide substrate scope, affording structurally diverse scaffolds under mild conditions. Furthermore, it provides an efficient route for synthesizing symmetrical urea derivatives and offers a potential pathway for directly synthesizing tryptanthrin and related bioactive molecules.
{"title":"Chemodivergent temperature-controlled switchable iron-catalysed annulation of o-vinylaniline with isatin derivatives†","authors":"Sakshi Singh , Samir Kumar Mondal , Shantanu Pal","doi":"10.1039/d5qo00626k","DOIUrl":"10.1039/d5qo00626k","url":null,"abstract":"<div><div>Chemodivergent approaches strive to enable achieving regioselective and site-divergent transformations of multiple products from identical, readily accessible starting materials by changing the reaction parameters, but are challenging due to the complexity of precisely controlling the chemodiversity. Herein, we report a novel FeCl<sub>3</sub>-catalyzed one-pot strategy involving switching the temperature to enable the selective synthesis of 5-methyl-7-phenyldibenzo[<em>b</em>,<em>h</em>][1,6] naphthy-ridin-6(5<em>H</em>)-one or 3-phenyl-1<em>H</em>-indole from o-vinylaniline and <em>N</em>-substituted isatin. Notably, the reaction exhibits temperature-controlled chemodivergence, selectively yielding either intramolecular or intermolecular products. This approach demonstrates a wide substrate scope, affording structurally diverse scaffolds under mild conditions. Furthermore, it provides an efficient route for synthesizing symmetrical urea derivatives and offers a potential pathway for directly synthesizing tryptanthrin and related bioactive molecules.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5445-5452"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144193343","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}
Pub Date : 2025-09-05Epub Date: 2025-06-19DOI: 10.1039/d5qo00808e
Shangyong Wu , Binbin Yuan , Yongke Lei , Xiaoli Su , Tristan von Münchow , João C. A. Oliveira , Xuewu Huang , Zhaojun Ding , Rongrong Xu , Lutz Ackermann , Jiayu Mo
In the realm of sustainable molecular synthesis, metallaelectro-catalysis has emerged as a highly potent platform over the past decade. While significant advancements have been achieved in this field, the development of strategies for late-stage C–H functionalization remains a formidable challenge. In this context, we present an electrochemical rhodium-catalyzed C–H activation strategy that facilitates the selective modification of bioactive compounds. The developed electrocatalysis strategy, enabling the efficient C–H/N–H activations and annulations with a variety of diaryl-, dialkyl-, and unsymmetric alkynes, demonstrates broad tolerance towards a range of medicinally relevant functional groups and thus provides expedient access to the modification of bioactive compounds.
{"title":"Rhodaelectro-catalyzed C–H activations directed by pharmacophores: enabling modification of bioactive compounds†","authors":"Shangyong Wu , Binbin Yuan , Yongke Lei , Xiaoli Su , Tristan von Münchow , João C. A. Oliveira , Xuewu Huang , Zhaojun Ding , Rongrong Xu , Lutz Ackermann , Jiayu Mo","doi":"10.1039/d5qo00808e","DOIUrl":"10.1039/d5qo00808e","url":null,"abstract":"<div><div>In the realm of sustainable molecular synthesis, metallaelectro-catalysis has emerged as a highly potent platform over the past decade. While significant advancements have been achieved in this field, the development of strategies for late-stage C–H functionalization remains a formidable challenge. In this context, we present an electrochemical rhodium-catalyzed C–H activation strategy that facilitates the selective modification of bioactive compounds. The developed electrocatalysis strategy, enabling the efficient C–H/N–H activations and annulations with a variety of diaryl-, dialkyl-, and unsymmetric alkynes, demonstrates broad tolerance towards a range of medicinally relevant functional groups and thus provides expedient access to the modification of bioactive compounds.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5566-5572"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144319460","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}
Pub Date : 2025-09-05Epub Date: 2025-06-11DOI: 10.1039/d5qo00681c
Sihan Zhou , Qingle Zeng
A highly efficient and straightforward strategy for the synthesis of benzothiadiazine 1-oxides has been developed, involving a copper(i)-catalyzed tandem C–N coupling/condensation cyclization of ortho-haloaryl organyl NH-sulfoximines and aromatic/aliphatic amidines. This protocol exhibits several notable advantages, including the absence of a requirement for an additional nitrogen source, a broad substrate scope, mild reaction conditions, and significant potential for application in the industrial production of benzothiadiazine 1-oxides.
{"title":"Copper(i)-catalyzed tandem C–N coupling/condensation cyclization for the synthesis of benzothiadiazine 1-oxides†","authors":"Sihan Zhou , Qingle Zeng","doi":"10.1039/d5qo00681c","DOIUrl":"10.1039/d5qo00681c","url":null,"abstract":"<div><div>A highly efficient and straightforward strategy for the synthesis of benzothiadiazine 1-oxides has been developed, involving a copper(<span>i</span>)-catalyzed tandem C–N coupling/condensation cyclization of <em>ortho</em>-haloaryl organyl NH-sulfoximines and aromatic/aliphatic amidines. This protocol exhibits several notable advantages, including the absence of a requirement for an additional nitrogen source, a broad substrate scope, mild reaction conditions, and significant potential for application in the industrial production of benzothiadiazine 1-oxides.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5519-5524"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144260761","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}
Pub Date : 2025-09-05Epub Date: 2025-06-04DOI: 10.1039/d5qo00667h
Xi-Ni Luo , Dong-Qing Yang , Hong-Lin Wu , Jia-Yao Feng , Sheng Du , Yu He , Rong-Nan Yi , Jun-Qi Zhang , Keqi Tang , Wen-Ting Wei
Photocatalytic radical-induced cyclization reactions offer an efficient paradigm for constructing aromatic rings due to their unique environmental friendliness, independence from electronic effects, and high functional group tolerance. However, the high reactivity of intermediates in radical reactions, particularly the challenges of controlling it proceeds in an orderly manner according to the expected pathway and the reaction terminates after the ring is formed, which leads to diminished precision in the construction of aromatic rings. Compared to traditional cyclization methods for synthesizing aromatic rings, photocatalysis enables direct cleavage of high-bond-energy chemical bonds under mild conditions, eliminating the need for high temperature, high pressure, or stoichiometric oxidants. Furthermore, photocatalytic systems can serve as a bridge to connect multiple reaction steps, thereby streamlining the process and enhancing efficiency. Recently, significant progress has been made in applying photocatalytic radical-induced cyclization for the construction of aromatic rings. However, to date, there has been no comprehensive summary of this area reported. In this review, we try to provide a comprehensive perspective on the construction of aromatic rings via photocatalytic radical-induced cyclization. The discussion is organized into five sections based on the type of aromatic ring formed: monoheteroatom-doped aromatic rings, diheteroatom-doped aromatic rings, triheteroatom-doped aromatic rings, all-carbon aromatic rings, and non-classical aromatic rings. This review is particularly focused on elucidating reaction mechanisms, the synergistic effect of catalysts and light sources, and the applications of this strategy in pharmaceutical synthesis and materials science.
{"title":"The construction of aromatic rings by photocatalytic radical-induced cyclization reactions","authors":"Xi-Ni Luo , Dong-Qing Yang , Hong-Lin Wu , Jia-Yao Feng , Sheng Du , Yu He , Rong-Nan Yi , Jun-Qi Zhang , Keqi Tang , Wen-Ting Wei","doi":"10.1039/d5qo00667h","DOIUrl":"10.1039/d5qo00667h","url":null,"abstract":"<div><div>Photocatalytic radical-induced cyclization reactions offer an efficient paradigm for constructing aromatic rings due to their unique environmental friendliness, independence from electronic effects, and high functional group tolerance. However, the high reactivity of intermediates in radical reactions, particularly the challenges of controlling it proceeds in an orderly manner according to the expected pathway and the reaction terminates after the ring is formed, which leads to diminished precision in the construction of aromatic rings. Compared to traditional cyclization methods for synthesizing aromatic rings, photocatalysis enables direct cleavage of high-bond-energy chemical bonds under mild conditions, eliminating the need for high temperature, high pressure, or stoichiometric oxidants. Furthermore, photocatalytic systems can serve as a bridge to connect multiple reaction steps, thereby streamlining the process and enhancing efficiency. Recently, significant progress has been made in applying photocatalytic radical-induced cyclization for the construction of aromatic rings. However, to date, there has been no comprehensive summary of this area reported. In this review, we try to provide a comprehensive perspective on the construction of aromatic rings <em>via</em> photocatalytic radical-induced cyclization. The discussion is organized into five sections based on the type of aromatic ring formed: monoheteroatom-doped aromatic rings, diheteroatom-doped aromatic rings, triheteroatom-doped aromatic rings, all-carbon aromatic rings, and non-classical aromatic rings. This review is particularly focused on elucidating reaction mechanisms, the synergistic effect of catalysts and light sources, and the applications of this strategy in pharmaceutical synthesis and materials science.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 20","pages":"Pages 5622-5643"},"PeriodicalIF":0.0,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144211686","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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