In recent years, carbon nitride-based photocatalysts have garnered significant attention for their role in facilitating organic transformations. As a solid-state sensitizer material, carbon nitride exhibits promising properties as a heterogeneous photocatalyst, making it suitable for a variety of organic reactions. Notably, its stability, water compatibility, and recoverability render it particularly appealing for organic transformations conducted in aqueous environments. Leveraging abundant and non-toxic water as a solvent aligns with green synthetic principles, promoting sustainable development. This review encompasses a range of organic transformations, including C–H functionalization, oxidation using oxygen, hydrogenation, and related sequential reactions, as well as cross-couplings conducted in aqueous media. Additionally, reactions employing water or heavy water as reactants to provide protons (or deuterium), electrons, and hydroxy groups are discussed. We anticipate that this summary will serve as a valuable resource for future studies aimed at advancing sustainable and environmentally friendly organic synthesis using carbon nitride photocatalysts.
{"title":"Recent advances on carbon nitride-based photocatalysts for organic transformations in aqueous media","authors":"Pengfei Zhou, Yunfei Cai, Yurong Tang","doi":"10.1039/d4qo00955j","DOIUrl":"https://doi.org/10.1039/d4qo00955j","url":null,"abstract":"In recent years, carbon nitride-based photocatalysts have garnered significant attention for their role in facilitating organic transformations. As a solid-state sensitizer material, carbon nitride exhibits promising properties as a heterogeneous photocatalyst, making it suitable for a variety of organic reactions. Notably, its stability, water compatibility, and recoverability render it particularly appealing for organic transformations conducted in aqueous environments. Leveraging abundant and non-toxic water as a solvent aligns with green synthetic principles, promoting sustainable development. This review encompasses a range of organic transformations, including C–H functionalization, oxidation using oxygen, hydrogenation, and related sequential reactions, as well as cross-couplings conducted in aqueous media. Additionally, reactions employing water or heavy water as reactants to provide protons (or deuterium), electrons, and hydroxy groups are discussed. We anticipate that this summary will serve as a valuable resource for future studies aimed at advancing sustainable and environmentally friendly organic synthesis using carbon nitride photocatalysts.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489453","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}
Reppe carbonylation is well-studied and extensively employed in industry, while the exploration and development of the Reppe sulfonylation reaction are still in their infancy. In this research, we have introduced a novel method for Reppe sulfonylation that incorporates sulfur dioxide without the requisites of metal catalysts, utilizing Brønsted bases instead. This technique presents a promising and efficient pathway for the synthesis of sulfonates, which possess wide-ranging applications. Our method facilitates the direct transformation of a vast spectrum of readily available alcohols (exceeding 70 variants) into their corresponding sulfonates, with yields varying from moderate to excellent. Furthermore, our approach is compatible with primary, secondary alkanols, and diols, efficiently yielding Reppe sulfonylation products. Significantly, this methodology is amenable to the late-stage functionalization of complex molecules, supporting a broad array of functional groups.
{"title":"Brønsted Base Catalyzed Reppe Sulfonylation Reaction","authors":"Xiaochun He, Xiaohong Wang, Fei Zhou, Hongzhuo Song, Xuemei Zhang, Zhong Lian","doi":"10.1039/d4qo00721b","DOIUrl":"https://doi.org/10.1039/d4qo00721b","url":null,"abstract":"Reppe carbonylation is well-studied and extensively employed in industry, while the exploration and development of the Reppe sulfonylation reaction are still in their infancy. In this research, we have introduced a novel method for Reppe sulfonylation that incorporates sulfur dioxide without the requisites of metal catalysts, utilizing Brønsted bases instead. This technique presents a promising and efficient pathway for the synthesis of sulfonates, which possess wide-ranging applications. Our method facilitates the direct transformation of a vast spectrum of readily available alcohols (exceeding 70 variants) into their corresponding sulfonates, with yields varying from moderate to excellent. Furthermore, our approach is compatible with primary, secondary alkanols, and diols, efficiently yielding Reppe sulfonylation products. Significantly, this methodology is amenable to the late-stage functionalization of complex molecules, supporting a broad array of functional groups.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489369","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 would like to take this opportunity to thank all of Organic Chemistry Frontiers’ reviewers for helping to preserve quality and integrity in chemical science literature. We would also like to highlight the Outstanding Reviewers for Organic Chemistry Frontiers in 2023.
{"title":"Outstanding Reviewers for Organic Chemistry Frontiers in 2023","authors":"","doi":"10.1039/d4qo90047b","DOIUrl":"https://doi.org/10.1039/d4qo90047b","url":null,"abstract":"We would like to take this opportunity to thank all of <em>Organic Chemistry Frontiers</em>’ reviewers for helping to preserve quality and integrity in chemical science literature. We would also like to highlight the Outstanding Reviewers for <em>Organic Chemistry Frontiers</em> in 2023.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489357","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 a catalytic synthesis of N-triflyl aldimines from aldehydes and triflylamide using imino-λ3-iodane generated in situ from iodosylarene precatalyst and triflylamide. In the present reaction, imino-λ3-iodane works as acid-base cooperative catalyst to activate aldehydes and triflylamide.
{"title":"Synthesis of N-triflyl aldimines catalyzed by imino-λ3-iodane","authors":"Shun Sunagawa, Yoko Tezuka, Akira Tsubouchi, Akira Yoshimura, Akio Saito","doi":"10.1039/d4qo00875h","DOIUrl":"https://doi.org/10.1039/d4qo00875h","url":null,"abstract":"We report a catalytic synthesis of <em>N</em>-triflyl aldimines from aldehydes and triflylamide using imino-<em>λ</em><small><sup>3</sup></small>-iodane generated in situ from iodosylarene precatalyst and triflylamide. In the present reaction, imino-<em>λ</em><small><sup>3</sup></small>-iodane works as acid-base cooperative catalyst to activate aldehydes and triflylamide.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489308","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}
Gairong Wang, Peng Guo, Guoliang Pu, Pan Wang, An-Jun Wang, Peijun Liu, Jia Jia, Xuefei Li, Chun-Yang He
The synergistic interplay between halogen bond and Ni catalysis under visible light irradiation has been explored. This reaction system enables the concurrent reduction of α-trifluoromethyl alkyl bromides and the cross-coupling of activated tetrahydrofuran (THF) with heterocycles in one pot. This strategic integration of nickel catalysts and visible light activation, complemented by the auxiliary effect of halogen bond, renders the transformation remarkably atom-economic and demonstrates exceptional functional group tolerance. The practical utility of this protocol has been further underscored through the direct modification of biologically active molecules.
{"title":"Catalytic Reduction of Trifluoromethylated Alkyl Bromides and Synthesis of Alkylated Heterocycles under Visible Irradiation: Synergetic Action of Halogen Bond and Ni Catalysis","authors":"Gairong Wang, Peng Guo, Guoliang Pu, Pan Wang, An-Jun Wang, Peijun Liu, Jia Jia, Xuefei Li, Chun-Yang He","doi":"10.1039/d4qo00966e","DOIUrl":"https://doi.org/10.1039/d4qo00966e","url":null,"abstract":"The synergistic interplay between halogen bond and Ni catalysis under visible light irradiation has been explored. This reaction system enables the concurrent reduction of α-trifluoromethyl alkyl bromides and the cross-coupling of activated tetrahydrofuran (THF) with heterocycles in one pot. This strategic integration of nickel catalysts and visible light activation, complemented by the auxiliary effect of halogen bond, renders the transformation remarkably atom-economic and demonstrates exceptional functional group tolerance. The practical utility of this protocol has been further underscored through the direct modification of biologically active molecules.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141463064","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}
Ning Wang, Ruzhao Chen, Zhe Chen, waken li, Xiuling Wen, Cunyuan Zhao, Zhuofeng Ke
Although the transition-metal-catalyzed cascade reaction of allylic alcohols has achieved great success, there are rare selective examples catalyzed only by bases. Here, We presented an efficient chemoselective catalytic system for the synthesis of valuable γ-indolation phenylpropanol and bis(indolyl)methane derivatives mediated by transition-metal-free base and tuned through alkali metal ion. This protocol having a wide range of substrates and functional group tolerance can be directly applied to the gram scale reactions and further transfers to useful intermediates. Experimental and theoretical studies have shown that cesium ions and sodium ions can precisely regulate the different hydrogen migration pathways of allylic alcohols.
{"title":"Alkali Ion Controlled Chemoselective Indolation of Allylic Alcohols by Base Catalysis","authors":"Ning Wang, Ruzhao Chen, Zhe Chen, waken li, Xiuling Wen, Cunyuan Zhao, Zhuofeng Ke","doi":"10.1039/d4qo00777h","DOIUrl":"https://doi.org/10.1039/d4qo00777h","url":null,"abstract":"Although the transition-metal-catalyzed cascade reaction of allylic alcohols has achieved great success, there are rare selective examples catalyzed only by bases. Here, We presented an efficient chemoselective catalytic system for the synthesis of valuable <em>γ</em>-indolation phenylpropanol and bis(indolyl)methane derivatives mediated by transition-metal-free base and tuned through alkali metal ion. This protocol having a wide range of substrates and functional group tolerance can be directly applied to the gram scale reactions and further transfers to useful intermediates. Experimental and theoretical studies have shown that cesium ions and sodium ions can precisely regulate the different hydrogen migration pathways of allylic alcohols.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141462693","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}
Alkenes are fundamental components in synthetic chemistry, extensively used in the production of complex molecules for pharmaceuticals, materials science, and agrochemicals. Nickel-catalyzed transformations of alkenes via nickelacycle intermediates, formed by the oxidative cyclization of alkenes with other π-components on Ni(0), offer a promising approach characterized by high atom and step economy. Although numerous C–C bond formation reactions involving nickelacycles have been widely studied, there is a notable scarcity of comprehensive reviews that focus on transformations of alkenes. Recent progress in ligand design has enhanced control reactivity and selectivity, enabling a variety of nickel-catalyzed couplings. These include reactions of alkenes with carbon dioxide, isocyanates, alkynes, α,β-unsaturated carbonyls, aldehydes, ketones, and imines. This lack of in-depth discussion highlights the need for a detailed review that encompasses recent advancements in this field. This review summarizes these recent developments in nickel-catalyzed transformations of alkenes via nickelacycles, highlighting the advantages and challenges of this innovative strategy. The goal is to inspire new researchers to explore and contribute to this dynamic field, emphasizing nickelacycle intermediates as versatile tools for effective reactions with various π-components and identifying them as promising avenues for future research.
{"title":"Catalytic Transformations of Alkenes via Nickelacycles","authors":"Meng-Ying Qian, Kai-Xiang Zhang, Li-Jun Xiao","doi":"10.1039/d4qo00737a","DOIUrl":"https://doi.org/10.1039/d4qo00737a","url":null,"abstract":"Alkenes are fundamental components in synthetic chemistry, extensively used in the production of complex molecules for pharmaceuticals, materials science, and agrochemicals. Nickel-catalyzed transformations of alkenes via nickelacycle intermediates, formed by the oxidative cyclization of alkenes with other π-components on Ni(0), offer a promising approach characterized by high atom and step economy. Although numerous C–C bond formation reactions involving nickelacycles have been widely studied, there is a notable scarcity of comprehensive reviews that focus on transformations of alkenes. Recent progress in ligand design has enhanced control reactivity and selectivity, enabling a variety of nickel-catalyzed couplings. These include reactions of alkenes with carbon dioxide, isocyanates, alkynes, α,β-unsaturated carbonyls, aldehydes, ketones, and imines. This lack of in-depth discussion highlights the need for a detailed review that encompasses recent advancements in this field. This review summarizes these recent developments in nickel-catalyzed transformations of alkenes via nickelacycles, highlighting the advantages and challenges of this innovative strategy. The goal is to inspire new researchers to explore and contribute to this dynamic field, emphasizing nickelacycle intermediates as versatile tools for effective reactions with various π-components and identifying them as promising avenues for future research.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141462560","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 a 1,3-heteroaryl acyloxylation of 3-substituted propargylic esters with readily available heteroarenes including indoles, pyrroles, furans and thiophenes under palladium catalysis. The heteroaryl-functionalized Z-enol ester products are obtained in a single step with complete levels of γ-regioselectivity and anti-hydroacetoxylation stereocontrol. The use of palladium-tri(2-furyl)phosphine complex in polyfluorinated alcoholic solvents has proven to be crucial to the reactivity of the desired pathway based on control experiments. High atom economy, mild conditions (30 °C) and broad functional group tolerance make this protocol attractive. Finally, the synthetic utility of this method is demonstrated by gram-scale synthesis and downstream derivatizations of the product.
{"title":"Palladium(II)-Catalyzed 1,3-Heteroaryl Acyloxylation of Propargylic Electrophiles","authors":"Shenghan Teng, Peiyao Liang, Lin Hu, Siyi Chen, Shoulei Wang, Wei Huang","doi":"10.1039/d4qo00869c","DOIUrl":"https://doi.org/10.1039/d4qo00869c","url":null,"abstract":"We report a 1,3-heteroaryl acyloxylation of 3-substituted propargylic esters with readily available heteroarenes including indoles, pyrroles, furans and thiophenes under palladium catalysis. The heteroaryl-functionalized Z-enol ester products are obtained in a single step with complete levels of γ-regioselectivity and anti-hydroacetoxylation stereocontrol. The use of palladium-tri(2-furyl)phosphine complex in polyfluorinated alcoholic solvents has proven to be crucial to the reactivity of the desired pathway based on control experiments. High atom economy, mild conditions (30 °C) and broad functional group tolerance make this protocol attractive. Finally, the synthetic utility of this method is demonstrated by gram-scale synthesis and downstream derivatizations of the product.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141461948","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}
Microwave assisted divergent domino reactions between cyclic 2-diazo-1,3-diketones and aniline derivatives selectively leading to either glutaramides, piperidino[1,2-a]benzimidazol-1-ones or N-cyclopentenyl benzimidazolones are described. This synthetic protocol features easy operation, shrort reaction time, and environmental friendliness.
{"title":"Green synthesis of glutaramides, piperidino[1,2-a]benzimidazol-1-ones and N-cyclopentenyl benzimidazolones enabled by microwave assisted domino reactions of cyclic 2-diazo-1,3-diketones with aniline derivatives","authors":"Cheng Zhao, Xiao-Wei Hu, Yi-Bing Xu, Xiong-Wei Liu, You-Ping Tian, Yun-Lin Liu","doi":"10.1039/d4qo00613e","DOIUrl":"https://doi.org/10.1039/d4qo00613e","url":null,"abstract":"Microwave assisted divergent domino reactions between cyclic 2-diazo-1,3-diketones and aniline derivatives selectively leading to either glutaramides, piperidino[1,2-a]benzimidazol-1-ones or N-cyclopentenyl benzimidazolones are described. This synthetic protocol features easy operation, shrort reaction time, and environmental friendliness.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141453101","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}
Long He, Xiaocheng Zhang, Sen Li, Xuexue Tian, Yimeng Han, Haitao Xie, Weiqing Xie
Herein, we present a novel approach to construct the A-B-C-D ring system of anislactone-type sesquiterpenoids. This innovative strategy involves a H2O2-mediated oxidative ring contraction reaction to form a 5/5 fused skeleton, while simultaneously generating contiguous quaternary carbon centers (CQCCs). Additionally, the γ-lactones (A- and D- rings) are assembled through Pummerer reaction initiated cyclization and sequential Mukaiyama hydration/translactonization, respectively. Despite our efforts to introduce a hydroxyl group at C7 via C-H oxidation, these endeavors ultimately proved unsuccessful.
{"title":"A Novel Approach to the Tetracyclic Frameworks of Anislactone-type Sesquiterpenoids","authors":"Long He, Xiaocheng Zhang, Sen Li, Xuexue Tian, Yimeng Han, Haitao Xie, Weiqing Xie","doi":"10.1039/d4qo00915k","DOIUrl":"https://doi.org/10.1039/d4qo00915k","url":null,"abstract":"Herein, we present a novel approach to construct the A-B-C-D ring system of anislactone-type sesquiterpenoids. This innovative strategy involves a H2O2-mediated oxidative ring contraction reaction to form a 5/5 fused skeleton, while simultaneously generating contiguous quaternary carbon centers (CQCCs). Additionally, the γ-lactones (A- and D- rings) are assembled through Pummerer reaction initiated cyclization and sequential Mukaiyama hydration/translactonization, respectively. Despite our efforts to introduce a hydroxyl group at C7 via C-H oxidation, these endeavors ultimately proved unsuccessful.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141453143","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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