H-bonded helically folded aromatic foldamers rely on the precise formation of H-bonds between each helicity codon and its neighboring codons to maintain their structure. We report here for the first time that the phenyl group, referred to as a non-helicity codon due to its inability to form H-bonds, does not necessarily disrupt the helical structure. Specifically, we modified our recently reported pyridine-based aquapentamers by sequentially replacing each of the five pyridine residues with a phenyl group, creating a series of five hybrid pentamers. The phenyl groups, unable to form H-bonds with the adjacent N-H bonds of the amides, introduce H-bond defects along the helical backbone. Despite these defects, three out of five pentamers still adopt a helical structure and function as highly selective and ultra-fast abiotic water channels, with the most efficient channel achieving a water transport rate of 1.8 × 109 H₂O s-1 per channel—approximately 30% of aquaporin Z’s capacity.
{"title":"Superfast and Highly Selective Water Transport by Hybrid Aquapentamers Incorporating a Non-Helicity Codon","authors":"Gaiping Cao, Zihong Yang, Huaiqing Zhao, Jie Shen, Wenju Chang, Zhiwei Liu, Huaqiang Zeng","doi":"10.1039/d4qo02231a","DOIUrl":"https://doi.org/10.1039/d4qo02231a","url":null,"abstract":"H-bonded helically folded aromatic foldamers rely on the precise formation of H-bonds between each helicity codon and its neighboring codons to maintain their structure. We report here for the first time that the phenyl group, referred to as a non-helicity codon due to its inability to form H-bonds, does not necessarily disrupt the helical structure. Specifically, we modified our recently reported pyridine-based aquapentamers by sequentially replacing each of the five pyridine residues with a phenyl group, creating a series of five hybrid pentamers. The phenyl groups, unable to form H-bonds with the adjacent N-H bonds of the amides, introduce H-bond defects along the helical backbone. Despite these defects, three out of five pentamers still adopt a helical structure and function as highly selective and ultra-fast abiotic water channels, with the most efficient channel achieving a water transport rate of 1.8 × 109 H₂O s-1 per channel—approximately 30% of aquaporin Z’s capacity.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"19 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142936511","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}
Ortho-alkylated phenols are widely exist innatural products and bioactive compounds. Here we have developed a mild, transition-metal-free approach for the C(sp3)-C(sp2) cross-coupling of alkenyl boronic acids with secondary alcohols via neighboring group activation, furnishing a serize of ortho-allylphenols. The C(sp³)-hydroxyl group was activated through intramolecular interaction with ortho-phenolic functional groups (triflyl, tert-butoxycarbonyl, phosphoryl, and cyclic carbonate). This method exhibits good substrate compatibility, allowing for the efficient synthesis of ortho-allyl phenols and subsequent transformation into high-value scaffolds
{"title":"Transition-metal-free C(sp3)-C(sp2) couplings with secondary alcohols and boronic acids via neighboring group activation","authors":"Xingxing Yang, Yourong Pan, Cheng Ren, Chengrui Hu, Feng Wan, Hongliang Duan, Chengxi Li","doi":"10.1039/d4qo02061h","DOIUrl":"https://doi.org/10.1039/d4qo02061h","url":null,"abstract":"Ortho-alkylated phenols are widely exist innatural products and bioactive compounds. Here we have developed a mild, transition-metal-free approach for the C(sp3)-C(sp2) cross-coupling of alkenyl boronic acids with secondary alcohols via neighboring group activation, furnishing a serize of ortho-allylphenols. The C(sp³)-hydroxyl group was activated through intramolecular interaction with ortho-phenolic functional groups (triflyl, tert-butoxycarbonyl, phosphoryl, and cyclic carbonate). This method exhibits good substrate compatibility, allowing for the efficient synthesis of ortho-allyl phenols and subsequent transformation into high-value scaffolds","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"30 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142936535","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 solid-state fluorescence of fluorophores is usually weakened or quenched by strong π-π interactions. Here, the solid-state fluorescence quantum yields (ΦSF) of tetrasubstituted tetrahydro-pyrimidines (TTHPs) are enhanced rather than decreased/or quenched by strong π-π interactions. All investigated TTHPs (5a−k) possess with aggregation-induced emission (AIE) characteristics: completely no emission in solutions owing to their soft, stero and low-conjugated molecular structures, but become emission upon aggregation, with ΦSF equal to 3%−87.7%, because of the formation of excellent through-bond/space/hyperconjugation-mixed electron cojugation system and radiative--transition-favored molecular packing modes as well as the restriction of molecular motions. Unexpectedly, achiral TTHPs aggregate via meso-enantiomers for 5k (both N1 and N3 atoms show pyramidal configuration) and via rac-enantiomers for other TTHPs (N1 shows racemic pyramidal inversion configurations and N3 shows planar configuration). Even more surprisingly, unlike conventional AIE fluorophores that can efficiently prevent cofacial π−π interaction, strong cofacial π−π interaction exists between the N1-inversion-based rac-enantiomers and can significantly enhance rather than decrease ΦSF values by efficiently decreasing knr values, which is first reported. Designing compounds with pyramidal inverstion might be an efficient stratgy to obtain highly emissive π−π stacking aggregates.
{"title":"Nitrogen-inversion-based racemate aggregation and interenantiomer -stacking-caused solid-state fluorescence enhancement","authors":"Zesheng Huang, Xiaoyi Qin, Yanshan Liu, Qiuhua Zhu","doi":"10.1039/d4qo02159b","DOIUrl":"https://doi.org/10.1039/d4qo02159b","url":null,"abstract":"The solid-state fluorescence of fluorophores is usually weakened or quenched by strong π-π interactions. Here, the solid-state fluorescence quantum yields (<em>Φ</em><small><sub>SF</sub></small>) of tetrasubstituted tetrahydro-pyrimidines (TTHPs) are enhanced rather than decreased/or quenched by strong π-π interactions. All investigated TTHPs (<strong>5a</strong>−<strong>k</strong>) possess with aggregation-induced emission (AIE) characteristics: completely no emission in solutions owing to their soft, stero and low-conjugated molecular structures, but become emission upon aggregation, with <em>Φ</em><small><sub>SF</sub></small> equal to 3%−87.7%, because of the formation of excellent through-bond/space/hyperconjugation-mixed electron cojugation system and radiative--transition-favored molecular packing modes as well as the restriction of molecular motions. Unexpectedly, achiral TTHPs aggregate via <em>meso</em>-enantiomers for <strong>5k</strong> (both N1 and N3 atoms show pyramidal configuration) and via <em>rac</em>-enantiomers for other TTHPs (N1 shows racemic pyramidal inversion configurations and N3 shows planar configuration). Even more surprisingly, unlike conventional AIE fluorophores that can efficiently prevent cofacial π−π interaction, strong cofacial π−π interaction exists between the N1-inversion-based <em>rac</em>-enantiomers and can significantly enhance rather than decrease <em>Φ</em><small><sub>SF</sub></small> values by efficiently decreasing <em>k</em><small><sub>nr</sub></small> values, which is first reported. Designing compounds with pyramidal inverstion might be an efficient stratgy to obtain highly emissive π−π stacking aggregates.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"452 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142935437","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 palladium-catalyzed asymmetric allylic alkylation of carbon-based pronucleophiles is a highly efficient and enantioselective strategy for the synthesis of pharmaceutically relevant molecules. While significant progress has been made in the allylation of azlactones to access valuable α-amino acids, there remains a notable gap in catalytic asymmetric transformations involving 2-alkyl-4-aryl-, 2,4-diaryl-, and 2,4-dialkyl-substituted azlactones. To address this challenge, we developed a palladium-catalyzed asymmetric allyl substitution of N-acyl phenylglycine N-hydroxyphthalimide esters with allyl acetates, featuring good yields, remarkable stereoselectivity, and a broad substrate scope. Furthermore, the product can be readily derivatized into diverse polyfunctional compounds that have great potential for the exploitation of pharmaceuticals and biologically active molecules.
{"title":"Pd-catalyzed asymmetric allylic alkylation of N-hydroxyphthalimide esters with allyl acetates","authors":"Yixuan Zheng, Xinhao Deng, Fei Zhao, Yuanyuan Peng, Qiongjiao Yan, Wei Wang, Fener Chen, Hui Zhou","doi":"10.1039/d4qo02257b","DOIUrl":"https://doi.org/10.1039/d4qo02257b","url":null,"abstract":"The palladium-catalyzed asymmetric allylic alkylation of carbon-based pronucleophiles is a highly efficient and enantioselective strategy for the synthesis of pharmaceutically relevant molecules. While significant progress has been made in the allylation of azlactones to access valuable α-amino acids, there remains a notable gap in catalytic asymmetric transformations involving 2-alkyl-4-aryl-, 2,4-diaryl-, and 2,4-dialkyl-substituted azlactones. To address this challenge, we developed a palladium-catalyzed asymmetric allyl substitution of N-acyl phenylglycine N-hydroxyphthalimide esters with allyl acetates, featuring good yields, remarkable stereoselectivity, and a broad substrate scope. Furthermore, the product can be readily derivatized into diverse polyfunctional compounds that have great potential for the exploitation of pharmaceuticals and biologically active molecules.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"41 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142935438","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}
Kai Jiang, Ziyan Zhao, Xiaodong Yin, Fangjun Chen, BiaoLin Yin
Excited-palladium catalysis has already been exploited to achieve 1,4-difunctionalization of dienes via the radical generation of allylpalladium intermediate. Herein, the nonactivated phenyl rings that are treated as the masked trienes, have accomplished dearomative 1,4-dicarbofunctionalization in the excited-palladium catalytic two- and three-component system. A wide range of alkyl bromides, and 1,3-dicarbonyl compounds, which play the roles of radical precursor and nucleophile respectively, were found to be suitable for this reaction. Various three-dimensional molecular architecture with multiple quaternary carbon centers were efficiently constructed through this mild reaction.
{"title":"Excited Pd-catalyzed dearomative 1,4-dicarbofunctionalization of nonactivated aromatic rings","authors":"Kai Jiang, Ziyan Zhao, Xiaodong Yin, Fangjun Chen, BiaoLin Yin","doi":"10.1039/d4qo02173h","DOIUrl":"https://doi.org/10.1039/d4qo02173h","url":null,"abstract":"Excited-palladium catalysis has already been exploited to achieve 1,4-difunctionalization of dienes via the radical generation of allylpalladium intermediate. Herein, the nonactivated phenyl rings that are treated as the masked trienes, have accomplished dearomative 1,4-dicarbofunctionalization in the excited-palladium catalytic two- and three-component system. A wide range of alkyl bromides, and 1,3-dicarbonyl compounds, which play the roles of radical precursor and nucleophile respectively, were found to be suitable for this reaction. Various three-dimensional molecular architecture with multiple quaternary carbon centers were efficiently constructed through this mild reaction.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"79 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142936536","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}
Zixuan Xie, Xiaoheng Ji, Xu Zeng, Daiki Shimizu, Takayuki Tanaka, Yutao Rao, Mingbo Zhou, Ling Xu, Atsuhiro Osuka, Jianxin Song
Oxidation of B-tolyl BIII 5,10,15-tritolylsubporphyrin with tris(4-bromophenyl)ammoniumyl hexachloroantimonate gave its cation radical instantaneously, which slowly dissociated to give BIII subporphyrin borenium hexachloroantimonate in 89% after stirring overnight. This is a much more convenient synthesis of BIII borenium cation. Oxidants such as tris(4-bromophenyl)ammonium tetrakis(perfluorophenyl)borate and AgSbF6 can be used for the synthesis of the borenium cation. Oxidation of B-tolyl BIII 5,10,15-trianisylsubporphyrin with AgSbF6 gave a cation radical that was stable at room temperature but dissociated to give the corresponding borenium cation upon refluxing in CH2Cl2, while B-tolyl BIII 5,10,15-tris(4-dibutylaminophenyl)subporphyrin was oxidized to give a cation radical that was easily oxidized to afford a quinonoidal dication. Oxidation of B-tolyl BIIIβ-hexaethyl-5,10,15-tri(4-diethylaminophenyl)subporphyrin with AgSbF6 gave a borenium cation instantaneously. As such, the reactivities of the cation radicals depend on the peripheral substituents.
{"title":"Cation Radicals, Borenium Cations, and Dication from Oxidation of B-Tolyl BIII Subporphyrins","authors":"Zixuan Xie, Xiaoheng Ji, Xu Zeng, Daiki Shimizu, Takayuki Tanaka, Yutao Rao, Mingbo Zhou, Ling Xu, Atsuhiro Osuka, Jianxin Song","doi":"10.1039/d4qo02291b","DOIUrl":"https://doi.org/10.1039/d4qo02291b","url":null,"abstract":"Oxidation of B-tolyl B<small><sup>III</sup></small> 5,10,15-tritolylsubporphyrin with tris(4-bromophenyl)ammoniumyl hexachloroantimonate gave its cation radical instantaneously, which slowly dissociated to give B<small><sup>III</sup></small> subporphyrin borenium hexachloroantimonate in 89% after stirring overnight. This is a much more convenient synthesis of B<small><sup>III</sup></small> borenium cation. Oxidants such as tris(4-bromophenyl)ammonium tetrakis(perfluorophenyl)borate and AgSbF<small><sub>6</sub></small> can be used for the synthesis of the borenium cation. Oxidation of B-tolyl B<small><sup>III</sup></small> 5,10,15-trianisylsubporphyrin with AgSbF<small><sub>6</sub></small> gave a cation radical that was stable at room temperature but dissociated to give the corresponding borenium cation upon refluxing in CH<small><sub>2</sub></small>Cl<small><sub>2</sub></small>, while B-tolyl B<small><sup>III</sup></small> 5,10,15-tris(4-dibutylaminophenyl)subporphyrin was oxidized to give a cation radical that was easily oxidized to afford a quinonoidal dication. Oxidation of B-tolyl B<small><sup>III</sup></small><em>β</em>-hexaethyl-5,10,15-tri(4-diethylaminophenyl)subporphyrin with AgSbF<small><sub>6</sub></small> gave a borenium cation instantaneously. As such, the reactivities of the cation radicals depend on the peripheral substituents.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"10 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929154","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}
In the field of modern biochemistry and drug development, the acquisition of homogeneous sugar complexes is crucial for evaluating their biophysical activities. These sugar complexes are essential for understanding biomacromolecule functions and serve as potential vaccine candidates. The synthesis of sugar conjugates is a key step in achieving this goal, and the selection of sugar donors and control of glycosylation reaction outcomes are particularly important in this process. Our recent research indicates that glycosyl PVB donors exhibit self-stability, high reactivity, and excellent yields when activated by NIS/TMSOTf promoters. Notably, glycosyl PVB donors can achieve similar glycosylation effects with I2 activation. This metal-free reaction condition is broadly applicable in the synthesis of various O-glycosides, N-glycosides, and the carbohydrate drug PG545 (an anti-tumor agent).
{"title":"2-(1-Phenylvinyl)benzoic acid as a Highly Active Leaving Group for Metal-Free Glycosylation","authors":"Qi Dai, Penghua Li, Yaran Cao, Xiangying Xie, Chen Zhang, Mingyue Zheng, Shen Haiwei","doi":"10.1039/d4qo02186j","DOIUrl":"https://doi.org/10.1039/d4qo02186j","url":null,"abstract":"In the field of modern biochemistry and drug development, the acquisition of homogeneous sugar complexes is crucial for evaluating their biophysical activities. These sugar complexes are essential for understanding biomacromolecule functions and serve as potential vaccine candidates. The synthesis of sugar conjugates is a key step in achieving this goal, and the selection of sugar donors and control of glycosylation reaction outcomes are particularly important in this process. Our recent research indicates that glycosyl PVB donors exhibit self-stability, high reactivity, and excellent yields when activated by NIS/TMSOTf promoters. Notably, glycosyl PVB donors can achieve similar glycosylation effects with I<small><sub>2</sub></small> activation. This metal-free reaction condition is broadly applicable in the synthesis of various O-glycosides, N-glycosides, and the carbohydrate drug PG545 (an anti-tumor agent).","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"20 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929155","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}
Xu-Lang Chen, Si-Qian Yu, Jia-Qi Liang, Xiaohuan Huang, Han-Yuan Gong
Bowl-shaped polycyclic aromatic hydrocarbons (PAHs) have garnered significant attention over the past decades due to their visually striking molecular architectures, along with their exceptional physical and chemical properties. These unique characteristics make them valuable scaffolds in supramolecular chemistry and materials science. A widely adopted strategy to further enhance the properties of PAHs involves the introduction of heteroatoms into their molecular framework. Specifically, nitrogen-doping has emerged as a powerful tool to fine-tune the electronic, structural, and chemical properties of bowl-shaped PAHs, imparting new functionalities. In recent years, nitrogen-containing bowl-shaped PAHs with increasingly diverse structures and properties have become a focal point of research in materials and supramolecular science. This paper provides a comprehensive review of the latest developments in the synthesis, structural characteristics, and supramolecular assembly of nitrogen-containing bowl-shaped PAHs, highlighting their growing importance in advanced material applications.
{"title":"Nitrogen-containing polycyclic aromatic hydrocarbons (PAHs) with bowl-shaped structures: synthesis, architecture, and applications","authors":"Xu-Lang Chen, Si-Qian Yu, Jia-Qi Liang, Xiaohuan Huang, Han-Yuan Gong","doi":"10.1039/d4qo01934b","DOIUrl":"https://doi.org/10.1039/d4qo01934b","url":null,"abstract":"Bowl-shaped polycyclic aromatic hydrocarbons (PAHs) have garnered significant attention over the past decades due to their visually striking molecular architectures, along with their exceptional physical and chemical properties. These unique characteristics make them valuable scaffolds in supramolecular chemistry and materials science. A widely adopted strategy to further enhance the properties of PAHs involves the introduction of heteroatoms into their molecular framework. Specifically, nitrogen-doping has emerged as a powerful tool to fine-tune the electronic, structural, and chemical properties of bowl-shaped PAHs, imparting new functionalities. In recent years, nitrogen-containing bowl-shaped PAHs with increasingly diverse structures and properties have become a focal point of research in materials and supramolecular science. This paper provides a comprehensive review of the latest developments in the synthesis, structural characteristics, and supramolecular assembly of nitrogen-containing bowl-shaped PAHs, highlighting their growing importance in advanced material applications.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"34 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917791","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 and efficient method for synthesizing carboxamides has been developed, utilizing a base-promoted Lossen rearrangement of hydroxylamine derivatives. In this reaction, the hydroxylamine derivatives are bench-top stable and easy to handle, allowing them to smoothly replace highly toxic isocyanate reagents by generating isocyanates in situ. This approach facilitates the straightforward formation of both C-P and C-C bonds. Furthermore, the mild reaction conditions, straightforward operational procedure, and broad substrate scope render this protocol highly practical and attractive.
{"title":"Metal-free synthesis of carboxamides via Lossen rearrangement","authors":"Chong Li, Yi-Fei Liu, Wei Yang, Lian-Jie Zhao, Lin-Yuan Song, Yu-Shuang Deng, Ke-Yu Mou, Jing-Wen Wang, Sheng Cao, Feng Li","doi":"10.1039/d4qo02155j","DOIUrl":"https://doi.org/10.1039/d4qo02155j","url":null,"abstract":"A novel and efficient method for synthesizing carboxamides has been developed, utilizing a base-promoted Lossen rearrangement of hydroxylamine derivatives. In this reaction, the hydroxylamine derivatives are bench-top stable and easy to handle, allowing them to smoothly replace highly toxic isocyanate reagents by generating isocyanates in situ. This approach facilitates the straightforward formation of both C-P and C-C bonds. Furthermore, the mild reaction conditions, straightforward operational procedure, and broad substrate scope render this protocol highly practical and attractive.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"73 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917792","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}
Xun Yang, Yuxuan Xiao, Ying Yin, Haiyan Li, Jiahui Du, Xin Li, Wengui Duan, Lin Yu
With increasing concerns regarding the energy crisis and environmental changes, the development of sunlight-based methods for organic synthesis has become imperative. We present a masking enone strategy that effectively suppresses side reactions associated with enone products, enabling the β-selective acylation of alkenes catalyzed by excited-state copper under sunlight or visible light. This reaction yields highly valuable α, β-unsaturated ketones, which can be readily transformed into important building blocks through various conversions. Notably, this method is characterized by its sustainable and eco-friendly energy source, mild reaction conditions, high compatibility with functional groups, and suitability for gram-scale synthesis, making it promising for late-stage modifications of complex molecules. Mechanistic studies indicate that the reaction proceeds via a free radical pathway.
{"title":"Visible-light or sunlight photoredox-catalyzed β-selective acylation of alkenes to access α, β-unsaturated ketones","authors":"Xun Yang, Yuxuan Xiao, Ying Yin, Haiyan Li, Jiahui Du, Xin Li, Wengui Duan, Lin Yu","doi":"10.1039/d4qo02101k","DOIUrl":"https://doi.org/10.1039/d4qo02101k","url":null,"abstract":"With increasing concerns regarding the energy crisis and environmental changes, the development of sunlight-based methods for organic synthesis has become imperative. We present a masking enone strategy that effectively suppresses side reactions associated with enone products, enabling the β-selective acylation of alkenes catalyzed by excited-state copper under sunlight or visible light. This reaction yields highly valuable α, β-unsaturated ketones, which can be readily transformed into important building blocks through various conversions. Notably, this method is characterized by its sustainable and eco-friendly energy source, mild reaction conditions, high compatibility with functional groups, and suitability for gram-scale synthesis, making it promising for late-stage modifications of complex molecules. Mechanistic studies indicate that the reaction proceeds via a free radical pathway.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"34 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917794","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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