Transition-metal-catalyzed hydrocarbonylation of alkenes has been widely studied, however, the hydrocarbonylation reaction that took place between two alkenes has been largely unexplored. Herein, we report a palladium-catalyzed hydrocarbonylative cross-coupling with two different alkenes to produce structurally diverse β-ketoaldehyde surrogates, which can be easily converted to different types of heterocycles including pyrazole, isoxazole and pyrimidine.
{"title":"Palladium-catalyzed hydrocarbonylative cross-coupling with two different alkenes","authors":"Hanmin Huang, Yi Chen, Jianing Wu, Yongzheng Ding","doi":"10.1039/d4qo01312c","DOIUrl":"https://doi.org/10.1039/d4qo01312c","url":null,"abstract":"Transition-metal-catalyzed hydrocarbonylation of alkenes has been widely studied, however, the hydrocarbonylation reaction that took place between two alkenes has been largely unexplored. Herein, we report a palladium-catalyzed hydrocarbonylative cross-coupling with two different alkenes to produce structurally diverse β-ketoaldehyde surrogates, which can be easily converted to different types of heterocycles including pyrazole, isoxazole and pyrimidine.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452373","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}
Due to the multifaceted reactivities of cyclopropenes, the divergent hydrofunctionalization of these compounds has recently attracted significant attention. Herein, we present a Pd-catalyzed hydrocyanation of cyclopropenes via aluminum Lewis acid-controlled divergent chemoselectivity. In this study, the presence of aluminum Lewis acid plays an pivotal role on the reaction pathway. In the absence of aluminum Lewis acid, the reaction predominantly yields ring-opening hydrocyanation products, whereas the addition of Lewis acid directs the formation of ring-retentive products.
{"title":"Lewis Acid-Controlled Pd-Catalyzed Chemodivergent Hydrocyanation of Cyclopropenes","authors":"Rongrong Yu, Song-Zhou Cai, Xianjie Fang","doi":"10.1039/d4qo01609b","DOIUrl":"https://doi.org/10.1039/d4qo01609b","url":null,"abstract":"Due to the multifaceted reactivities of cyclopropenes, the divergent hydrofunctionalization of these compounds has recently attracted significant attention. Herein, we present a Pd-catalyzed hydrocyanation of cyclopropenes via aluminum Lewis acid-controlled divergent chemoselectivity. In this study, the presence of aluminum Lewis acid plays an pivotal role on the reaction pathway. In the absence of aluminum Lewis acid, the reaction predominantly yields ring-opening hydrocyanation products, whereas the addition of Lewis acid directs the formation of ring-retentive products.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452375","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}
Lizhi Fang, Xiaowen Guan, Yanling Shen, Dayang Zhou, Long Chen, Xiaochuan Chen, Wanhua Wu, Leyong Wang, Cheng Yang
Halogen-substituted pillar[5]arenes exhibited hindered hydroquinone subunit flipping, enabling enantioseparation. An enantiopure conformer demonstrated a dissymmetric factor of 0.012 and an enantioselective binding ratio exceeding 1.92. Complexation with L-serine induced an enantiopreference in the pillar[5]arene, which persisted for a certain period after chiral inducer removal and reversed upon the addition of D-serine. This induced enantiopreference was subsequently transferred to a chromophore guest, achieving a multi-step chiral transfer process. This approach offers a potential alternative to traditional chiral HPLC methods, enabling the manipulation of chiral recognition and transfer through chiral inducers.
{"title":"Multistep Chirality Transfer and Racemization Kinetics of Pillar [5]arenes by Tuning the Halogen Substituents on the Rims","authors":"Lizhi Fang, Xiaowen Guan, Yanling Shen, Dayang Zhou, Long Chen, Xiaochuan Chen, Wanhua Wu, Leyong Wang, Cheng Yang","doi":"10.1039/d4qo01799d","DOIUrl":"https://doi.org/10.1039/d4qo01799d","url":null,"abstract":"Halogen-substituted pillar[5]arenes exhibited hindered hydroquinone subunit flipping, enabling enantioseparation. An enantiopure conformer demonstrated a dissymmetric factor of 0.012 and an enantioselective binding ratio exceeding 1.92. Complexation with L-serine induced an enantiopreference in the pillar[5]arene, which persisted for a certain period after chiral inducer removal and reversed upon the addition of D-serine. This induced enantiopreference was subsequently transferred to a chromophore guest, achieving a multi-step chiral transfer process. This approach offers a potential alternative to traditional chiral HPLC methods, enabling the manipulation of chiral recognition and transfer through chiral inducers.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452378","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 present a metal-free and gentle three-component reaction involving vinylarenes, NHC-BH3 complexes, hydrosilanes, and 4-cyanopyridine. This versatile reaction encompasses a broad scope, encompassing over 40 examples of vinylarenes, NHC-BH3 complexes, and hydrosilanes, leading to the synthesis of diverse β-pyridinyl boranes and β-pyridinyl silanes. Furthermore, we demonstrate the potential of this methodology by functionalizing pharmaceutical molecules, showcasing its practical applications
{"title":"Metal Free Visible-Light-Induced Borylative/Silylative Pyridylation of Vinylarenes","authors":"Yiting Zhou, Bin Liu","doi":"10.1039/d4qo01702a","DOIUrl":"https://doi.org/10.1039/d4qo01702a","url":null,"abstract":"We present a metal-free and gentle three-component reaction involving vinylarenes, NHC-BH3 complexes, hydrosilanes, and 4-cyanopyridine. This versatile reaction encompasses a broad scope, encompassing over 40 examples of vinylarenes, NHC-BH3 complexes, and hydrosilanes, leading to the synthesis of diverse β-pyridinyl boranes and β-pyridinyl silanes. Furthermore, we demonstrate the potential of this methodology by functionalizing pharmaceutical molecules, showcasing its practical applications","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452377","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}
Trichloromethyl compounds are essential constituents in synthetic and medicinal chemistry. Hydrotrichloromethylation of alkenes represents the most straightforward approach for synthesizing trichloromethyl compounds. Nonetheless, the applicability of prior synthesis methodologies in this regard was notably constrained by the superstoichiometric use of excessive radical initiators and the formation of alkene polymers or dichloromethylation by-products. Herein, innovative and facile photocatalytic hydrotrichloromethylation of unactivated alkenes using chloroform via base-enabled photoinduced single-electron transfer is demonstrated. This strategy offers an expedited way of synthesizing trichloromethyl compounds with broad applicability and mild conditions while addressing the limitations of previous synthesis methods. Meanwhile, mechanistic studies support the process of chloroform deprotonation followed by oxidation.
{"title":"Photocatalytic hydrotrichloromethylation of unactivated alkenes with chloroform","authors":"dawei gong, Caiyu Gao, Qixuan Li, Yufei Li, lina zhao, Degong Kong","doi":"10.1039/d4qo01496k","DOIUrl":"https://doi.org/10.1039/d4qo01496k","url":null,"abstract":"Trichloromethyl compounds are essential constituents in synthetic and medicinal chemistry. Hydrotrichloromethylation of alkenes represents the most straightforward approach for synthesizing trichloromethyl compounds. Nonetheless, the applicability of prior synthesis methodologies in this regard was notably constrained by the superstoichiometric use of excessive radical initiators and the formation of alkene polymers or dichloromethylation by-products. Herein, innovative and facile photocatalytic hydrotrichloromethylation of unactivated alkenes using chloroform via base-enabled photoinduced single-electron transfer is demonstrated. This strategy offers an expedited way of synthesizing trichloromethyl compounds with broad applicability and mild conditions while addressing the limitations of previous synthesis methods. Meanwhile, mechanistic studies support the process of chloroform deprotonation followed by oxidation.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452376","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}
Xiang Liu, Jiawei He, Keyu Lin, Xingyue Wang, Hua Cao
Due to their low activation energy barriers, small strained carbocyclic systems have always been fascinating building blocks in organic chemistry. Among them, BCBs, as the smallest bicyclic carbocycle, exhibits a molecular structure, bond angles, and orbital hybridization significantly different from those of strain-free hydrocarbons, resulting in unique reactivity. In recent years, Lewis acid-catalyzed strain-release cycloaddition reactions have made BCBs powerful synthetic tools, utilized in various laboratories to expand into other ring systems. This review primarily focuses on the latest developments in Lewis acid-catalyzed strain-release cycloaddition reactions of BCBs, highlighting the applications and limitations of this catalytic system in different types of cycloaddition reactions, providing professionals and non-professionals in the field with valuable insights and new inspiration.
{"title":"State-of-the-Art Strategies for Lewis Acid-Catalyzed Strain-Release Cycloadditions of Bicyclo[1.1.0]butanes (BCBs)","authors":"Xiang Liu, Jiawei He, Keyu Lin, Xingyue Wang, Hua Cao","doi":"10.1039/d4qo01741b","DOIUrl":"https://doi.org/10.1039/d4qo01741b","url":null,"abstract":"Due to their low activation energy barriers, small strained carbocyclic systems have always been fascinating building blocks in organic chemistry. Among them, BCBs, as the smallest bicyclic carbocycle, exhibits a molecular structure, bond angles, and orbital hybridization significantly different from those of strain-free hydrocarbons, resulting in unique reactivity. In recent years, Lewis acid-catalyzed strain-release cycloaddition reactions have made BCBs powerful synthetic tools, utilized in various laboratories to expand into other ring systems. This review primarily focuses on the latest developments in Lewis acid-catalyzed strain-release cycloaddition reactions of BCBs, highlighting the applications and limitations of this catalytic system in different types of cycloaddition reactions, providing professionals and non-professionals in the field with valuable insights and new inspiration.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452426","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 regioselective hydro-functionalization reaction is a powerful method to convert readily available alkynes into structurally diverse olefins. Such an efficient syn-1,2-hydroarylation of yne-acetates is described herein using aryl diazonium salts and silanes as aryl and hydride sources, respectively. The transformation shows excellent functional group tolerance and applications to late-stage functionalization, providing a straightforward entry to trisubstituted allyl acetates. DFT analysis sheds light on the mechanism, particularly on the role of DMSO solvent in assisting the Si–H bond cleavage.
{"title":"Regioselective syn-1,2-Hydroarylation of Internal Alkynes","authors":"Shubham Dutta, Manoj Sethi, Avijit Maity, Aradhana Sahoo, Vincent Gandon, Akhila Kumar Sahoo","doi":"10.1039/d4qo01715c","DOIUrl":"https://doi.org/10.1039/d4qo01715c","url":null,"abstract":"The regioselective hydro-functionalization reaction is a powerful method to convert readily available alkynes into structurally diverse olefins. Such an efficient syn-1,2-hydroarylation of yne-acetates is described herein using aryl diazonium salts and silanes as aryl and hydride sources, respectively. The transformation shows excellent functional group tolerance and applications to late-stage functionalization, providing a straightforward entry to trisubstituted allyl acetates. DFT analysis sheds light on the mechanism, particularly on the role of DMSO solvent in assisting the Si–H bond cleavage.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142449842","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}
Mintu Rehman, D. Sajib, Rasajna Madhusudhana, Rajendar Goreti
LiTMP-LiBr complex facilitates a novel cross-ester coupling of 2-methoxy o-toluate esters to directly yield isocoumarin without the formation of any carbonyl intermediate is demonstrated. Aggregation plays a pivotal role in driving proximity-induced lateral lithiation, and expediting acylation. Apart from many natural products precursors synthesis of (+)- and (-)-lunatinins is showed.
{"title":"LiTMP-LiBr Complex-Induced Lateral Lithiation and Cross Ester Condensation: Direct Access to Isocoumarins from 2-methoxy o-Toluate Esters","authors":"Mintu Rehman, D. Sajib, Rasajna Madhusudhana, Rajendar Goreti","doi":"10.1039/d4qo01678e","DOIUrl":"https://doi.org/10.1039/d4qo01678e","url":null,"abstract":"LiTMP-LiBr complex facilitates a novel cross-ester coupling of 2-methoxy o-toluate esters to directly yield isocoumarin without the formation of any carbonyl intermediate is demonstrated. Aggregation plays a pivotal role in driving proximity-induced lateral lithiation, and expediting acylation. Apart from many natural products precursors synthesis of (+)- and (-)-lunatinins is showed.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142448437","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 selective oxidation of cyclohexene is rather challenging due to its allylic C-H and C=C bond two reactive centers. It is great significant to achieve highly selective oxidation towards the two reactive centers through regulating catalytic system. Herein, the selective oxidation towards allylic C-H and C=C bond reactive sites of cyclohexene was achieved by using CuCl2 and VCl3 as catalyst respectively in the presence of tert-butyl hydroperoxide (TBHP). CuCl2-catalyzed oxidation of cyclohexene mainly yielded oxidation products at allylic position, while VCl3-catalyzed oxidation of cyclohexene mainly yielded epoxidation products at C=C bond. The two different reaction mechanisms are mainly due to the different roles of t-BuOO• radical in the respective catalytic systems. From EPR (Electron Paramagnetic Resonance) characterizations, it could be known that the amount of t-BuOO• radicals in the CuCl2 catalytic system is much lower than that of in the VCl3 system. The two different mechanisms were proposed by means of 18O2 experiments, KIE kinetic and EPR. It revealed that CuCl2 catalyst could rapidly generate the t-BuOO• radical, which undergoes a bimolecular decay to produce O2. The oxygen combines with the allyl radical of cyclohexene to produce the oxidized product at allylic reactive center. In contrast, VCl3 catalyst promoted the generation of t-BuOO• radical, which reacted with C=C bond of cyclohexene to yield epoxide directly.
{"title":"Unravelling the different pathways of cyclohexene oxidation via peroxyl radical generated from tert-butyl hydroperoxide (TBHP) by various metal salts","authors":"Lu-Jian Zhou, Xiao-Hui Liu, Hanwen Zhang, Can Xue, Han-Kang Zhong, Xiantai Zhou","doi":"10.1039/d4qo01681e","DOIUrl":"https://doi.org/10.1039/d4qo01681e","url":null,"abstract":"The selective oxidation of cyclohexene is rather challenging due to its allylic C-H and C=C bond two reactive centers. It is great significant to achieve highly selective oxidation towards the two reactive centers through regulating catalytic system. Herein, the selective oxidation towards allylic C-H and C=C bond reactive sites of cyclohexene was achieved by using CuCl2 and VCl3 as catalyst respectively in the presence of tert-butyl hydroperoxide (TBHP). CuCl2-catalyzed oxidation of cyclohexene mainly yielded oxidation products at allylic position, while VCl3-catalyzed oxidation of cyclohexene mainly yielded epoxidation products at C=C bond. The two different reaction mechanisms are mainly due to the different roles of t-BuOO• radical in the respective catalytic systems. From EPR (Electron Paramagnetic Resonance) characterizations, it could be known that the amount of t-BuOO• radicals in the CuCl2 catalytic system is much lower than that of in the VCl3 system. The two different mechanisms were proposed by means of 18O2 experiments, KIE kinetic and EPR. It revealed that CuCl2 catalyst could rapidly generate the t-BuOO• radical, which undergoes a bimolecular decay to produce O2. The oxygen combines with the allyl radical of cyclohexene to produce the oxidized product at allylic reactive center. In contrast, VCl3 catalyst promoted the generation of t-BuOO• radical, which reacted with C=C bond of cyclohexene to yield epoxide directly.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142448928","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}
Arnab Dutta, Krzysztof Dzieszkowski, Marco Farinone, Łukasz Orzeł, Krzysztof Kruczała, Monika Kijewska, Miłosz Pawlicki
A precise design of unsaturated systems remains an important factor that determines the quality of formed products based on a specific spatial orientation, but also defining the available -electron density open for postsynthetic modulation via a redox change. Three strictly defined reagents showing a different degree of flexibility, but also introducing two mutual orientations of reacting ends (parallel and obtuse) determine the quality of formed products obtained via an intramolecular or an intermolecular reaction. The redox activated transformation of mono- and double-looped systems results in a dissimilar oxidation state of a strongly pi-conjugated dication (2 electron process) or a cation-radical (1 electron process) derived from the difference in dynamic of the skeleton documented for monomer and dimer, respectively.
{"title":"Folding of a Dynamic Macrocyclic System to Stabilize its Cation Radical State","authors":"Arnab Dutta, Krzysztof Dzieszkowski, Marco Farinone, Łukasz Orzeł, Krzysztof Kruczała, Monika Kijewska, Miłosz Pawlicki","doi":"10.1039/d4qo01566e","DOIUrl":"https://doi.org/10.1039/d4qo01566e","url":null,"abstract":"A precise design of unsaturated systems remains an important factor that determines the quality of formed products based on a specific spatial orientation, but also defining the available -electron density open for postsynthetic modulation via a redox change. Three strictly defined reagents showing a different degree of flexibility, but also introducing two mutual orientations of reacting ends (parallel and obtuse) determine the quality of formed products obtained via an intramolecular or an intermolecular reaction. The redox activated transformation of mono- and double-looped systems results in a dissimilar oxidation state of a strongly pi-conjugated dication (2 electron process) or a cation-radical (1 electron process) derived from the difference in dynamic of the skeleton documented for monomer and dimer, respectively.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142448142","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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