Qiping He, Wenxin Yan, Xianglin Yu, Xinxiang Huang, Chang Liu, Yinchun Jiao, Yi Jin
Herein, we report a applicable method for metal-catalyzed para-Csp2−H functionalization of arylamines through photoinduced ligand-to-metal charge transfer (LMCT). The Photo-LMCT-homolysis mode allows Sc−N complexes to form nitrogen radical intermediates, which are then isomerized into aryl radicals and prepared for subsequent radical coupling. A selective construction of C−O, C−S, C−Se, and C−C bonds has been achieved, and these reactions offer operationally simple, low-catalyst, and highly regioselective procedures for accessing valuable arylamine functionalization in a single step.
{"title":"LMCT-Homolysis-Enabled C−H Functionalization of Arylamines","authors":"Qiping He, Wenxin Yan, Xianglin Yu, Xinxiang Huang, Chang Liu, Yinchun Jiao, Yi Jin","doi":"10.1039/d4qo02146k","DOIUrl":"https://doi.org/10.1039/d4qo02146k","url":null,"abstract":"Herein, we report a applicable method for metal-catalyzed para-Csp2−H functionalization of arylamines through photoinduced ligand-to-metal charge transfer (LMCT). The Photo-LMCT-homolysis mode allows Sc−N complexes to form nitrogen radical intermediates, which are then isomerized into aryl radicals and prepared for subsequent radical coupling. A selective construction of C−O, C−S, C−Se, and C−C bonds has been achieved, and these reactions offer operationally simple, low-catalyst, and highly regioselective procedures for accessing valuable arylamine functionalization in a single step.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142905509","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
While there is a large literature on the use of trivalent phosphines in the activation of electrophilic unsaturated reagents, the application of such derivatives as photoorganoctatalysts for the generation of radical intermediates has received attention only in the recent decade. The present review aims to provide a detailed description of the phosphine-mediated photocatalysed and photoredox catalyzed protocols for the formation of both carbon-carbon and carbon-heteroatom bonds proposed in the last decade.
{"title":"Recent advances in visible-light driven phosphine-mediated transformations","authors":"Jiaxu Feng, Luca Nicchio, Liting Liu, Kui Lu, Yingying Wu, Stefano Protti, Xia Zhao","doi":"10.1039/d4qo02079k","DOIUrl":"https://doi.org/10.1039/d4qo02079k","url":null,"abstract":"While there is a large literature on the use of trivalent phosphines in the activation of electrophilic unsaturated reagents, the application of such derivatives as photoorganoctatalysts for the generation of radical intermediates has received attention only in the recent decade. The present review aims to provide a detailed description of the phosphine-mediated photocatalysed and photoredox catalyzed protocols for the formation of both carbon-carbon and carbon-heteroatom bonds proposed in the last decade.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"26 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142905508","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Melina Maag, Linus B. Dittmer, Elena Michel, Stephen Hashmi, Alexandra Mackenroth, Martin C. Dietl, Frank - Rominger, Matthias Rudolph, Andreas Dreuw
Herein we disclose a systematic evaluation of the scope and limitations for the use of alkynyl triazenes for the synthesis of cyano-substituted cyclopropanes and cyclopropenes. The method is based on the formation of a cyanocarbene by cleavage of the N1-N2 bond of the alkynyl triazene precursor under UV light, which then reacts with a styrene or alkyne to the respective products making this a simple approach avoiding metals typically used in related reactions of organic azides. Different substituents on the triazene moiety, N-terminus and styrene/alkyne were investigated concerning their influence on the yield and diastereoselectivity with respect to the resulting cyclopropanes. The study revealed that electron-rich aryl substituents at the alkynyl triazenes enable a good diastereomeric excess favouring the anti-diastereomer. Accompanying computational studies revealed that this diastereomeric preference can be qualitatively predicted from the relative stability of the singlet and triplet states of the cyanocarbene, as well as the dispersive attraction between the carbene and the olefin.
{"title":"Scope and Mechanistic Insight into the Chemistry of Cyanocarbenes derived from Alkynyl Triazenes by UV Irradiation","authors":"Melina Maag, Linus B. Dittmer, Elena Michel, Stephen Hashmi, Alexandra Mackenroth, Martin C. Dietl, Frank - Rominger, Matthias Rudolph, Andreas Dreuw","doi":"10.1039/d4qo02023e","DOIUrl":"https://doi.org/10.1039/d4qo02023e","url":null,"abstract":"Herein we disclose a systematic evaluation of the scope and limitations for the use of alkynyl triazenes for the synthesis of cyano-substituted cyclopropanes and cyclopropenes. The method is based on the formation of a cyanocarbene by cleavage of the N1-N2 bond of the alkynyl triazene precursor under UV light, which then reacts with a styrene or alkyne to the respective products making this a simple approach avoiding metals typically used in related reactions of organic azides. Different substituents on the triazene moiety, N-terminus and styrene/alkyne were investigated concerning their influence on the yield and diastereoselectivity with respect to the resulting cyclopropanes. The study revealed that electron-rich aryl substituents at the alkynyl triazenes enable a good diastereomeric excess favouring the anti-diastereomer. Accompanying computational studies revealed that this diastereomeric preference can be qualitatively predicted from the relative stability of the singlet and triplet states of the cyanocarbene, as well as the dispersive attraction between the carbene and the olefin.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"93 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142905511","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Single electron reduction of the Caryl−F bond is quite challenging due to its high reduction potential. Herein, we report an arenethiolate-catalyzed single electron reduction of the Caryl−F bond to access oxindoles. A variety of oxindoles are provided in moderate to excellent yields through a single electron reduction/cyclization/single electron oxidation process. Furthermore, the 1,5-HAT of inert C−H could be achieved with this method. A plausible pathway with the arenethiolate as a SET catalyst is proposed on the basis of mechanistic studies.
{"title":"Arenethiolate-catalyzed Caryl−F bond activation: Synthesis of oxindoles","authors":"Shengyun Liu, Mingying Li, Wei Xiao, Jie Wu","doi":"10.1039/d4qo01888e","DOIUrl":"https://doi.org/10.1039/d4qo01888e","url":null,"abstract":"Single electron reduction of the Caryl−F bond is quite challenging due to its high reduction potential. Herein, we report an arenethiolate-catalyzed single electron reduction of the Caryl−F bond to access oxindoles. A variety of oxindoles are provided in moderate to excellent yields through a single electron reduction/cyclization/single electron oxidation process. Furthermore, the 1,5-HAT of inert C−H could be achieved with this method. A plausible pathway with the arenethiolate as a SET catalyst is proposed on the basis of mechanistic studies.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"15 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142905510","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A novel copper-catalyzed C-O coupling reaction promoted by electromagnetic milling (EMM) has been reported for the mild and efficient synthesis of various diaryl ethers. This transformation could be realized without solvent, no additional heating, and short reaction time, which features a wide substrate scope, good functional group tolerance, and efficient gram-scale synthesis. A ligand derivated from the oxalic diamide was synthesized and utilized in the solid-state coupling, which exhibited excellent activity to the C-O bond formation under solid state. Control experiments via infrared (IR) spectroscopy showed the possible formation of Cu(I)-O intermediates with the high-speed rotating electromagnetic rod in the magnetic field. Additionally, it opens up extensive possibilities for the chemical bond activation and construction under multi energy-field coupling.
{"title":"Electromagnetic milling promoted mechanochemical Copper-Catalyzed C-O coupling reaction for diaryl ether formation","authors":"Zhaoxuan Zeng, Zhe Tian, Zhihan Zhang, Hongzhen Sun, Qing Liu, Lizhi Zhang, Fachao Yan, Zengdian Zhao, Hui Liu","doi":"10.1039/d4qo01909a","DOIUrl":"https://doi.org/10.1039/d4qo01909a","url":null,"abstract":"A novel copper-catalyzed C-O coupling reaction promoted by electromagnetic milling (EMM) has been reported for the mild and efficient synthesis of various diaryl ethers. This transformation could be realized without solvent, no additional heating, and short reaction time, which features a wide substrate scope, good functional group tolerance, and efficient gram-scale synthesis. A ligand derivated from the oxalic diamide was synthesized and utilized in the solid-state coupling, which exhibited excellent activity to the C-O bond formation under solid state. Control experiments via infrared (IR) spectroscopy showed the possible formation of Cu(I)-O intermediates with the high-speed rotating electromagnetic rod in the magnetic field. Additionally, it opens up extensive possibilities for the chemical bond activation and construction under multi energy-field coupling.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"87 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142888110","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
We report on a catalytic divergent C–H alkylation of 4-quinolones with diazo compounds where the reaction pathways are controlled by a reaction solvent. Cp*Rh(III)-catalyzed site-selective C−H alkylation was carried out in dichloromethane to produce C2-alkylated 4-quinolones. C(2)−H alkylation and sequential [1,3]-heteroarene rearrangement were achieved by utilizing EtOH/DMSO solvent in the same catalytic system at 70°C, allowing valuable 4-quinolones bearing an all-carbon quaternary center at the 2-position to be efficiently synthesized in a one-pot operation. By combining experimental results and computational studies, we propose an unprecedented DMSO-promoted Truce-Smiles rearrangement.
{"title":"Solvent-controlled catalytic divergent C–H alkylation of quinolones driven by unusual DMSO-promoted 1,3-heteroarene migration","authors":"Ye Lim Kim, Yuri Yun, Seoung-Mi Choi, Ju Hyun Kim","doi":"10.1039/d4qo01980f","DOIUrl":"https://doi.org/10.1039/d4qo01980f","url":null,"abstract":"We report on a catalytic divergent C–H alkylation of 4-quinolones with diazo compounds where the reaction pathways are controlled by a reaction solvent. Cp*Rh(III)-catalyzed site-selective C−H alkylation was carried out in dichloromethane to produce C2-alkylated 4-quinolones. C(2)−H alkylation and sequential [1,3]-heteroarene rearrangement were achieved by utilizing EtOH/DMSO solvent in the same catalytic system at 70°C, allowing valuable 4-quinolones bearing an all-carbon quaternary center at the 2-position to be efficiently synthesized in a one-pot operation. By combining experimental results and computational studies, we propose an unprecedented DMSO-promoted Truce-Smiles rearrangement.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"63 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142887223","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A novel cobalt-catalyzed 1,2-diazidation of 1‑aryl-1,3-dienes by using TMSN3 as azide source has been reported. A series of vicinal diazides containing unsaturated bonds that are amenable to further functionalization were synthesised with excellent regioselectivity and stereoselectivity under mild conditions. Preliminary mechanistic studies suggest that the reaction proceeds via a single electron transfer/radical addition/group transfer relay process.
{"title":"Cobalt-catalyzed regioselective diazidation of 1‑aryl-1,3-dienes enabled by a single electron transfer/radical addition/group transfer relay process","authors":"Chifan Zhu, Junju Mai, Xiao-Jing Li, Mingyuan Shi, Xiasen Dong, Huinan Fu, Mei-Hua Shen, Hua-Dong Xu","doi":"10.1039/d4qo02180k","DOIUrl":"https://doi.org/10.1039/d4qo02180k","url":null,"abstract":"A novel cobalt-catalyzed 1,2-diazidation of 1‑aryl-1,3-dienes by using TMSN3 as azide source has been reported. A series of vicinal diazides containing unsaturated bonds that are amenable to further functionalization were synthesised with excellent regioselectivity and stereoselectivity under mild conditions. Preliminary mechanistic studies suggest that the reaction proceeds via a single electron transfer/radical addition/group transfer relay process.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"33 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142879894","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A highly efficient catalytic enantioselective double annulation protocol has been developed for the asymmetric synthesis of hetero[7]helicenes. This method involves a sequential chiral phosphoric acid (CPA)-catalyzed three-component double Povarov reaction with a pentacyclic diamine followed by aromatization, which yielded various bispyridine-containing hetero[7]helicenes with good yields and excellent enantioselectivity. Notably, two distinct oxidative aromatization methods have been developed to selectively afford hetero[7]helicenes with either mono-amido or bis-amido substitutions at the peri-positions. Extensive derivatizations of these chiral heterohelicene products, along with detailed studies of their photophysical and chiroptical properties, underscore the significance of this method.
{"title":"Diverse Enantioselective Synthesis of Hetero[7]helicenes via an Organocatalyzed Double Annulation Strategy","authors":"Tianren Qin, Wansen Xie, Wei Liu, Xiaoyu Yang","doi":"10.1039/d4qo02188f","DOIUrl":"https://doi.org/10.1039/d4qo02188f","url":null,"abstract":"A highly efficient catalytic enantioselective double annulation protocol has been developed for the asymmetric synthesis of hetero[7]helicenes. This method involves a sequential chiral phosphoric acid (CPA)-catalyzed three-component double Povarov reaction with a pentacyclic diamine followed by aromatization, which yielded various bispyridine-containing hetero[7]helicenes with good yields and excellent enantioselectivity. Notably, two distinct oxidative aromatization methods have been developed to selectively afford hetero[7]helicenes with either mono-amido or bis-amido substitutions at the peri-positions. Extensive derivatizations of these chiral heterohelicene products, along with detailed studies of their photophysical and chiroptical properties, underscore the significance of this method.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"149 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142879897","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Manuel Buendía, Anton J Stasyuk, Salvatore Filippone, Nazario Martín, Miquel Solà
Supramolecular chemistry of carbon-based materials provides a variety of chemical structures with potential applications in materials science and biomedicine. Here, we explore the supramolecular complexation of fullerenes C60 and C70, highlighting the ability of molecular nanographene tweezers to capture these structures. The binding constant for the CNG-1⸧C70 complex was significantly higher than for CNG-1⸧C60, showing a clear selectivity for the more π-extended C70. DFT calculations confirmed these experimental results by showing that the interaction energy of C70 with CNG-1 is more than 5 kcal/mol higher than that of C60. Theoretical calculations predict that the dispersion interaction provides about 58-59% of the total interaction energy, followed by electrostatic attraction with 26% and orbital interactions, which contribute 15-16%. The racemic nanographene tweezers effectively recognize fullerene molecules and hold promise for future applications in chiral molecule recognition.
{"title":"All-carbon supramolecular complexation of a bilayer molecular nanographene with [60] and [70]fullerenes","authors":"Manuel Buendía, Anton J Stasyuk, Salvatore Filippone, Nazario Martín, Miquel Solà","doi":"10.1039/d4qo02071e","DOIUrl":"https://doi.org/10.1039/d4qo02071e","url":null,"abstract":"Supramolecular chemistry of carbon-based materials provides a variety of chemical structures with potential applications in materials science and biomedicine. Here, we explore the supramolecular complexation of fullerenes C<small><sub>60</sub></small> and C<small><sub>70,</sub></small> highlighting the ability of molecular nanographene tweezers to capture these structures. The binding constant for the <strong>CNG-1⸧C<small><sub>70</sub></small></strong> complex was significantly higher than for <strong>CNG-1⸧C<small><sub>60</sub></small></strong>, showing a clear selectivity for the more π-extended C<small><sub>70</sub></small>. DFT calculations confirmed these experimental results by showing that the interaction energy of C<small><sub>70</sub></small> with <strong>CNG-1</strong> is more than 5 kcal/mol higher than that of C<small><sub>60</sub></small>. Theoretical calculations predict that the dispersion interaction provides about 58-59% of the total interaction energy, followed by electrostatic attraction with 26% and orbital interactions, which contribute 15-16%. The racemic nanographene tweezers effectively recognize fullerene molecules and hold promise for future applications in chiral molecule recognition.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142879845","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The transition-metal-catalyzed intermolecular three-component dearomative difunctionalization of indoles in a one-pot fashion remains largely unexplored. Herein, we present a novel Ni-catalyzed dearomative alkylborylation of indoles utilizing a ligand-enabled, directing group-assisted strategy. This regio- and diastereoselective reaction efficiently converts readily accessible indoles into valuable C3-borylated and C2-alkylated indolines. Additionally, We established a practical one-pot procedure for accessing valuable 2,3-disubstituted indoles with boron retained by combining this protocol with the subsequent oxidation of the resulting indolines. The robustness of this protocol is demonstrated through gram-scale reactions, facile late-stage decoration of complex drug-like molecules, and various downstream diversifications.
{"title":"Amino Alcohol Ligand-enabled Ni-Catalyzed Regio- and Diastereoselective Dearomative Borylalkylation of Indoles","authors":"Jiaxin Wang, Xuelong Zhang, Aichen Li, Rui He, Surong Zhang, Xiangyue Li, Lanlan Zhang, Guodong Ju, Chao Wang","doi":"10.1039/d4qo02187h","DOIUrl":"https://doi.org/10.1039/d4qo02187h","url":null,"abstract":"The transition-metal-catalyzed intermolecular three-component dearomative difunctionalization of indoles in a one-pot fashion remains largely unexplored. Herein, we present a novel Ni-catalyzed dearomative alkylborylation of indoles utilizing a ligand-enabled, directing group-assisted strategy. This regio- and diastereoselective reaction efficiently converts readily accessible indoles into valuable C3-borylated and C2-alkylated indolines. Additionally, We established a practical one-pot procedure for accessing valuable 2,3-disubstituted indoles with boron retained by combining this protocol with the subsequent oxidation of the resulting indolines. The robustness of this protocol is demonstrated through gram-scale reactions, facile late-stage decoration of complex drug-like molecules, and various downstream diversifications.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"83 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142879896","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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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