A straightforward approach for the assemble of 2,3,5-trisubstituted 1H-pyrroles via a base-mediated [3+2] cycloaddition of 1-arylpropynes with nitriles has been reported through the alkali metal salts promoted C(sp3)-H functionalization. This reaction features transition metal-free catalyst, facile starting materials and wide substrate scope. Moreover, the biological evaluation revealed that these pyrrole products exhibit the antiproliferative activities of MDA-MB-231, SGC-7901, and HCT-116 cells, which provides a potential applications in pharmaceutical chemistry.
{"title":"Synthesis and antiproliferative activities of 2,3,5-trisubstituted 1H-pyrroles via formal [3+2] cycloaddition of 1-arylpropynes and nitriles","authors":"Dandan He, Ling Li, Xiong Wen, Luxiang Yin, Jue Li, Sha Wu, Huili Li, Fei Jiang, Xiangchun Shen","doi":"10.1039/d4qo01999g","DOIUrl":"https://doi.org/10.1039/d4qo01999g","url":null,"abstract":"A straightforward approach for the assemble of 2,3,5-trisubstituted 1H-pyrroles via a base-mediated [3+2] cycloaddition of 1-arylpropynes with nitriles has been reported through the alkali metal salts promoted C(sp3)-H functionalization. This reaction features transition metal-free catalyst, facile starting materials and wide substrate scope. Moreover, the biological evaluation revealed that these pyrrole products exhibit the antiproliferative activities of MDA-MB-231, SGC-7901, and HCT-116 cells, which provides a potential applications in pharmaceutical chemistry.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"3 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142797514","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}
Biquan Xiong, Siya Zheng, Weifeng Xu, Yu Liu, Longzhi Zhu, Kewen Tang, Zelin Sun, Wai-Yeung Raymond Wong
A novel and facile copper-catalyzed phosphorothiolation and seleno(telluro)phosphorylation of vinylsulfonium salts with P(III)-nucleophiles for constructing C-Z-P(V) bonds (Z = S, Se, Te) by activating selenium, tellurium and sulfur powder in-situ has been established. The phosphorylation process in this system may involve the Michaelis-Arbuzov rearrangement as the initial step. Vinylsulfonium salts with various substituents and different types of P(III)-nucleophiles demonstrated excellent substrate suitability, resulting in the synthesis of the expected products with moderate to good yields. The model reaction is readily scalable to gram-level experiments under optimized conditions. Additionally, a possible mechanism for this transformation was proposed based on insights gained from stepwise control experiments and 31P NMR tracking experiments. To the best of our knowledge, this is the first method to activate inorganic tellurium in-situ using a phosphorylation source to form P-Te bonds directly. The P-Te compounds synthesized via this method exhibit superior activity against methicillin-resistant Staphylococcus aureus (MRSA).
{"title":"Copper-Catalyzed Phosphorothiolation/Seleno(Telluro)phosphorylation of Vinylsulfonium Salts with P(III)-nucleophiles via the Insertion of Elemental Sulfur/Selenium/Tellurium","authors":"Biquan Xiong, Siya Zheng, Weifeng Xu, Yu Liu, Longzhi Zhu, Kewen Tang, Zelin Sun, Wai-Yeung Raymond Wong","doi":"10.1039/d4qo02154a","DOIUrl":"https://doi.org/10.1039/d4qo02154a","url":null,"abstract":"A novel and facile copper-catalyzed phosphorothiolation and seleno(telluro)phosphorylation of vinylsulfonium salts with P(III)-nucleophiles for constructing C-Z-P(V) bonds (Z = S, Se, Te) by activating selenium, tellurium and sulfur powder in-situ has been established. The phosphorylation process in this system may involve the Michaelis-Arbuzov rearrangement as the initial step. Vinylsulfonium salts with various substituents and different types of P(III)-nucleophiles demonstrated excellent substrate suitability, resulting in the synthesis of the expected products with moderate to good yields. The model reaction is readily scalable to gram-level experiments under optimized conditions. Additionally, a possible mechanism for this transformation was proposed based on insights gained from stepwise control experiments and 31P NMR tracking experiments. To the best of our knowledge, this is the first method to activate inorganic tellurium in-situ using a phosphorylation source to form P-Te bonds directly. The P-Te compounds synthesized via this method exhibit superior activity against methicillin-resistant Staphylococcus aureus (MRSA).","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"20 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142797515","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 difunctionalization of olefins as an effective synthetic strategy has garnered significant attention among organic synthetic chemists, thus enabling complex molecular scaffolds to be assembled in a single step from readily accessible feedstock chemicals. Herein, a nickel-catalyzed reductive difunctionalization of BN-heterocyclic alkenes has been developed. A variety of BN-heterocycles were synthesized utilizing the specific characteristics of selected difunctionalization reactions, thereby facilitating the synthesis of a wider range of BN-heterocycles through further conversions and applications.
{"title":"Nickel-Catalyzed Reductive Difunctionalization of BN-heterocyclic Olefins","authors":"Chaokun Li, Kui Yu, Kai Yang, Qiuling Song","doi":"10.1039/d4qo02032d","DOIUrl":"https://doi.org/10.1039/d4qo02032d","url":null,"abstract":"The difunctionalization of olefins as an effective synthetic strategy has garnered significant attention among organic synthetic chemists, thus enabling complex molecular scaffolds to be assembled in a single step from readily accessible feedstock chemicals. Herein, a nickel-catalyzed reductive difunctionalization of BN-heterocyclic alkenes has been developed. A variety of BN-heterocycles were synthesized utilizing the specific characteristics of selected difunctionalization reactions, thereby facilitating the synthesis of a wider range of BN-heterocycles through further conversions and applications.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"18 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793698","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 method was developed using LuCl3/ZnI2 to cocatalyze the 1,1-diboration of simple terminal alkynes, producing from moderate-to-good yields of 1,1-diborylalkenes. Large-scale synthesis and further transformations indicate that this method has potential practical applications. Isotopic labeling experiments, and control experiments are used to elucidate the reaction mechanism.
{"title":"LuCl3/ZnI2 cocatalyzed 1,1-diborylation of terminal alkynes to 1,1-diborylalkenes with pinacolborane","authors":"Rongrong Zhou, Wenli Wang, Jianping Zhang, Qi Wang, Ziyan Chen, Yinlin Shao, Fangjun Zhang","doi":"10.1039/d4qo01796j","DOIUrl":"https://doi.org/10.1039/d4qo01796j","url":null,"abstract":"A method was developed using LuCl3/ZnI2 to cocatalyze the 1,1-diboration of simple terminal alkynes, producing from moderate-to-good yields of 1,1-diborylalkenes. Large-scale synthesis and further transformations indicate that this method has potential practical applications. Isotopic labeling experiments, and control experiments are used to elucidate the reaction mechanism.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"18 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793704","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}
Hui Li, Yan Dong, RiQiang Li, Yan Zhang, Shengyong Liu and Wei Tian
Correction for ‘Hierarchical supramolecular assembly based on metal coordination of asymmetric ligand pairs and host–guest recognition’ by Hui Li et al., Org. Chem. Front., 2025, https://doi.org/10.1039/D4QO01926A.
{"title":"Correction: Hierarchical supramolecular assembly based on metal coordination of asymmetric ligand pairs and host–guest recognition","authors":"Hui Li, Yan Dong, RiQiang Li, Yan Zhang, Shengyong Liu and Wei Tian","doi":"10.1039/D4QO90098G","DOIUrl":"10.1039/D4QO90098G","url":null,"abstract":"<p >Correction for ‘Hierarchical supramolecular assembly based on metal coordination of asymmetric ligand pairs and host–guest recognition’ by Hui Li <em>et al.</em>, <em>Org. Chem. Front.</em>, 2025, https://doi.org/10.1039/D4QO01926A.</p>","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":" 1","pages":" 369-369"},"PeriodicalIF":4.6,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/qo/d4qo90098g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142783069","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ju Ho Yang, Ju Hyun Oh, Seung-Ryong Kwon and Sung Kuk Kim
Correction for ‘Calix[4]pyrrole bis-crowns as ion pair receptors: cation selectivity modulated by counter anions’ by Ju Ho Yang et al., Org. Chem. Front., 2024, 11, 6096–6103, https://doi.org/10.1039/D4QO01401D.
{"title":"Correction: Calix[4]pyrrole bis-crowns as ion pair receptors: cation selectivity modulated by counter anions","authors":"Ju Ho Yang, Ju Hyun Oh, Seung-Ryong Kwon and Sung Kuk Kim","doi":"10.1039/D4QO90099E","DOIUrl":"10.1039/D4QO90099E","url":null,"abstract":"<p >Correction for ‘Calix[4]pyrrole bis-crowns as ion pair receptors: cation selectivity modulated by counter anions’ by Ju Ho Yang <em>et al.</em>, <em>Org. Chem. Front.</em>, 2024, <strong>11</strong>, 6096–6103, https://doi.org/10.1039/D4QO01401D.</p>","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":" 1","pages":" 368-368"},"PeriodicalIF":4.6,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/qo/d4qo90099e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142783018","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hypseudone A (1), a hyperforin-derived caged PPAP (polycyclic polyprenylated acylphloroglucinol) together with three biosynthetic precursors (2–4), were identified from Hypericum pseudohenryi. Compound 1 was characterized as a new type of caged PPAP with an unprecedented tricyclo[5.2.1.03,8]decane skeleton. Biogenetically, 2–4 were originated from additional prenylation of hyperforin or its analogues at C-3 and the caged core of 1 was further generated through an undescribed cyclization mode of an oxygenated prenyl at C-3 and C-9. Their structure elucidations were achieved by NMR spectroscopy, X-ray diffraction, ECD calculations and further consolidated through biosynthetic considerations assisted by chemical shift calculations and DP4+ analysis. Compounds 1 and 3 exhibited remarkable neurite outgrowth-promoting and acetylcholinesterase inhibitory activities, respectively.
{"title":"Hypseudone A, a Hyperforin-Derived Polycyclic Polyprenylated Acylphloroglucinol with Caged Skeleton from Hypericum pseudohenryi","authors":"Gang Xu, Yan-Song Ye, Na-Na Jiang","doi":"10.1039/d4qo01955e","DOIUrl":"https://doi.org/10.1039/d4qo01955e","url":null,"abstract":"Hypseudone A (<strong>1</strong>), a hyperforin-derived caged PPAP (polycyclic polyprenylated acylphloroglucinol) together with three biosynthetic precursors (<strong>2</strong>–<strong>4</strong>), were identified from <em>Hypericum pseudohenryi</em>. Compound <strong>1</strong> was characterized as a new type of caged PPAP with an unprecedented tricyclo[5.2.1.0<small><sup>3,8</sup></small>]decane skeleton. Biogenetically, <strong>2</strong>–<strong>4</strong> were originated from additional prenylation of hyperforin or its analogues at C-3 and the caged core of <strong>1</strong> was further generated through an undescribed cyclization mode of an oxygenated prenyl at C-3 and C-9. Their structure elucidations were achieved by NMR spectroscopy, X-ray diffraction, ECD calculations and further consolidated through biosynthetic considerations assisted by chemical shift calculations and DP4+ analysis. Compounds <strong>1</strong> and <strong>3</strong> exhibited remarkable neurite outgrowth-promoting and acetylcholinesterase inhibitory activities, respectively.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"81 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142777053","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 development of novel fluorinated building blocks establishes a crucial basis for the synthesis of fluorinated compounds. CF3-containing 1,4-diketones could be a new class of fluorinated synthons. Here we report the first synthesis of α-CF3-1,4-diketones from commercially available aldehydes and 2-bromo-3,3,3-trifluoro-1-propene (BTP) by a cascade hydrogen atom transfer (HAT) process employing tetrabutylammonium decatungstate (TBADT) as a photocatalyst. Notably, this cascade HAT methodology effectively circumvents the common issue of defluorination that typically occurs in previously reported systems. Additionally, the newly synthesized α-CF3-1,4-diketones could be applied as starting materials for the construction of CF3-containing heterocycles, thereby expanding the prospects for developing novel pharmaceuticals.
{"title":"Photocatalyzed cascade hydrogen atom transfer for the construction of α-CF3-1,4-diketones","authors":"Xiao-Ya Yuan, Jing-Fei Zheng, Xinyu Ma, Xianqiang Huang, Qiyan Lv, Kai Sun, Xiaolan Chen, Lingbo Qu, Bing Yu","doi":"10.1039/d4qo01973c","DOIUrl":"https://doi.org/10.1039/d4qo01973c","url":null,"abstract":"The development of novel fluorinated building blocks establishes a crucial basis for the synthesis of fluorinated compounds. CF<small><sub>3</sub></small>-containing 1,4-diketones could be a new class of fluorinated synthons. Here we report the first synthesis of α-CF<small><sub>3</sub></small>-1,4-diketones from commercially available aldehydes and 2-bromo-3,3,3-trifluoro-1-propene (BTP) by a cascade hydrogen atom transfer (HAT) process employing tetrabutylammonium decatungstate (TBADT) as a photocatalyst. Notably, this cascade HAT methodology effectively circumvents the common issue of defluorination that typically occurs in previously reported systems. Additionally, the newly synthesized α-CF<small><sub>3</sub></small>-1,4-diketones could be applied as starting materials for the construction of CF<small><sub>3</sub></small>-containing heterocycles, thereby expanding the prospects for developing novel pharmaceuticals.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"27 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142777050","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}
Herein, visible-light-driven radical-radical cross-coupling for the construction of C(sp3)-S bond to afford various cyanoalkyl thioethers through EDA complex promoted C-C and C-H bond cleavage is described. The photoactivation of a transiently assembled chromophore between thiolate anions and cycloketone oxime esters is critical to the generation of C(sp3)-S bond. Notably, we also realize the in situ formed EDA complex-mediated 1,3-hydrogen atom transfer (HAT) to construct diverse thioethers under transtion-metal- and photocatalyst-free conditions. This synthetic method features easily available substrates, wide substrate scope, and mild reaction conditions, which has potential to be used for the preparation of valuable sulfides.
{"title":"Visible-light-induced radical C(sp3)-S coupling for the synthesis of cyanoalkyl thioethers","authors":"Zhi-Qiang Zhu, Xiao-Wen Zheng, Dong-Liang Zhang, Xiao-Long Huang, Qian-Qian Xu, Zong-Bo Xie, Zhang-Gao Le","doi":"10.1039/d4qo01994f","DOIUrl":"https://doi.org/10.1039/d4qo01994f","url":null,"abstract":"Herein, visible-light-driven radical-radical cross-coupling for the construction of C(sp3)-S bond to afford various cyanoalkyl thioethers through EDA complex promoted C-C and C-H bond cleavage is described. The photoactivation of a transiently assembled chromophore between thiolate anions and cycloketone oxime esters is critical to the generation of C(sp3)-S bond. Notably, we also realize the in situ formed EDA complex-mediated 1,3-hydrogen atom transfer (HAT) to construct diverse thioethers under transtion-metal- and photocatalyst-free conditions. This synthetic method features easily available substrates, wide substrate scope, and mild reaction conditions, which has potential to be used for the preparation of valuable sulfides.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"2 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142777051","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}
Jiangbo Wu, Mingtong Ji, Zhiming Li, Shengyi Tu, Zhihe Cen, Kai Huang, Yan Wang, Chang-Wu Zheng, Xiaoyu Wu
The nucleophilic activation of ketones containing a tethered hydroxyl group by borinic acid, through the formation of an unprecedented tetracoordinated boron enolate complex, is presented. The in situ-generated boron enolates are captured by electrophilic isatin imines, which are activated by chiral copper-based catalysts. This reaction accommodates a wide range of substrates, producing a series of 3-substituted 3-amino-2-oxindoles with a C3-tetrasubstituted stereogenic center, all in excellent yields and enantioselectivities. A plausible model for chiral induction in this reaction is proposed. The method's utility is further demonstrated by a gram-scale reaction and subsequent elaboration of the Mannich adducts.
{"title":"Enantioselective Mannich Reaction of Ketone Enolates with Imines through Cooperative B/Cu Catalysis","authors":"Jiangbo Wu, Mingtong Ji, Zhiming Li, Shengyi Tu, Zhihe Cen, Kai Huang, Yan Wang, Chang-Wu Zheng, Xiaoyu Wu","doi":"10.1039/d4qo02046d","DOIUrl":"https://doi.org/10.1039/d4qo02046d","url":null,"abstract":"The nucleophilic activation of ketones containing a tethered hydroxyl group by borinic acid, through the formation of an unprecedented tetracoordinated boron enolate complex, is presented. The in situ-generated boron enolates are captured by electrophilic isatin imines, which are activated by chiral copper-based catalysts. This reaction accommodates a wide range of substrates, producing a series of 3-substituted 3-amino-2-oxindoles with a C3-tetrasubstituted stereogenic center, all in excellent yields and enantioselectivities. A plausible model for chiral induction in this reaction is proposed. The method's utility is further demonstrated by a gram-scale reaction and subsequent elaboration of the Mannich adducts.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"66 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142777052","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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