Guang-Feng Jin, Fang Wang, F. Ekkehardt Hahn, Ying-Feng Han
A series of tetrakisimidazolium salts bearing two di(phenylimidazolium)amine groups linked by differently substituted anthracenes has been prepared. These are H4-1a(PF6)4 (anthracene bridge), H4-1b(PF6)4 (phenyl-anthracene-phenyl bridge), H4-1c(PF6)4 (anthracene-phenyl bridge) and H4-1d(PF6)4 (anthracene-phenyl-anthracene bridge). X-ray crystallography showed that those ligand precursors having the di(phenylimidazolium)amine connected directly to the anthracene experience restricted rotation about the N−Canthracene bond. Depending on their flexibility, the reaction of the tetrakisimidazolium salts with Ag2O followed by transmetalation with [AuCl(THT)] yielded octanuclear ([Au8(1a)4](PF6)8), tetranuclear ([Au4(1b)2](PF6)4), hexanuclear ([Au6(1c)3](PF6)6) or octanuclear ([Au8(1d)4](PF6)8) assemblies, demonstrating the direct bonding strategy can be employed for the selective synthesis of polynuclear poly-NHC (NHC = N-heterocyclic carbene) metallosupramolecular assemblies.
{"title":"The Flexibility of Tetra(N-Heterocyclic Carbene) Ligands Controls the Nuclearity and Geometry of Polynuclear MI‒NHC Assemblies","authors":"Guang-Feng Jin, Fang Wang, F. Ekkehardt Hahn, Ying-Feng Han","doi":"10.1002/anie.202502081","DOIUrl":"https://doi.org/10.1002/anie.202502081","url":null,"abstract":"A series of tetrakisimidazolium salts bearing two di(phenylimidazolium)amine groups linked by differently substituted anthracenes has been prepared. These are H4-1a(PF6)4 (anthracene bridge), H4-1b(PF6)4 (phenyl-anthracene-phenyl bridge), H4-1c(PF6)4 (anthracene-phenyl bridge) and H4-1d(PF6)4 (anthracene-phenyl-anthracene bridge). X-ray crystallography showed that those ligand precursors having the di(phenylimidazolium)amine connected directly to the anthracene experience restricted rotation about the N−Canthracene bond. Depending on their flexibility, the reaction of the tetrakisimidazolium salts with Ag2O followed by transmetalation with [AuCl(THT)] yielded octanuclear ([Au8(1a)4](PF6)8), tetranuclear ([Au4(1b)2](PF6)4), hexanuclear ([Au6(1c)3](PF6)6) or octanuclear ([Au8(1d)4](PF6)8) assemblies, demonstrating the direct bonding strategy can be employed for the selective synthesis of polynuclear poly-NHC (NHC = N-heterocyclic carbene) metallosupramolecular assemblies.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"183 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660757","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}
Chengying Zhou, Weitian Qin, Canhui Tu, Yunxuan Chen, Shaomin Fu, Bo Liu
Euphane triterpenoids are widely distributed in nature and show various intriguing bioactivities, but relatively few synthetic routes to them have been described. Here we report asymmetric convergent total syntheses of euphanes involving two triterpenoids and two nortriterpenoids: euphol, 25,26,27-trisnor-3β-hydroxy-euphan-24-al, euphorbiumrin D and oxo-tirucall-7-ene-3,20-dione. The syntheses employ an enantioselective Antilla allylboration and intramolecular radical cyclization to construct ring A, a palladium-catalyzed Liebeskind stannane-thioester coupling to connect ring A with the bicyclic CD system, and a novel radical cascade with metal-catalyzed hydrogen atom transfer (MHAT) to complete the polycyclic architecture. The late-stage syntheses of both triterpenoids feature a diimide reduction and a MHAT/1,5-hydrogen transfer cascade to diastereoselectively forge the C20 and C17 stereogenic centers.
{"title":"Total Synthesis of Euphane Triterpenoids Using Metal-Catalyzed Hydrogen Atom Transfer","authors":"Chengying Zhou, Weitian Qin, Canhui Tu, Yunxuan Chen, Shaomin Fu, Bo Liu","doi":"10.1002/anie.202503943","DOIUrl":"https://doi.org/10.1002/anie.202503943","url":null,"abstract":"Euphane triterpenoids are widely distributed in nature and show various intriguing bioactivities, but relatively few synthetic routes to them have been described. Here we report asymmetric convergent total syntheses of euphanes involving two triterpenoids and two nortriterpenoids: euphol, 25,26,27-trisnor-3β-hydroxy-euphan-24-al, euphorbiumrin D and oxo-tirucall-7-ene-3,20-dione. The syntheses employ an enantioselective Antilla allylboration and intramolecular radical cyclization to construct ring A, a palladium-catalyzed Liebeskind stannane-thioester coupling to connect ring A with the bicyclic CD system, and a novel radical cascade with metal-catalyzed hydrogen atom transfer (MHAT) to complete the polycyclic architecture. The late-stage syntheses of both triterpenoids feature a diimide reduction and a MHAT/1,5-hydrogen transfer cascade to diastereoselectively forge the C20 and C17 stereogenic centers.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"34 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660759","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}
Jiaxin Ma, Shengnan Fan, Cong Shao, Lizhe Wang, Yuan Dong, Guosheng Niu, Zongxiu Nie, Shiyong Yang, Jizheng Wang, Haixia Yang
Lead halide perovskite solar cells (PSCs) have made significant progress due to their low cost and high efficiency. However, the long-term stability and lead toxicity of PSCs remain a huge challenge for further commercialization. Herein, we designed a multifunctional additive PAE with photosensitive properties to overcome these difficulties. A unique double-chain copolymer network can be constructed via in situ polymerization induced by ultraviolet (UV) light. The multiple active sites in the polymer chains can passivate various defects and enhance charge transfer. Meanwhile, the vast network provides an effective defense for perovskite to stabilize the internal structure and resist harsh external environments, thus delaying the degradation of devices and maximizing the suppression of toxic lead leakage. Remarkably, the devices protected by the network achieved a champion power conversion efficiency (PCE) of 26.20% (certified as 25.69%), the unencapsulated devices suppressed 80% of lead leakage and the encapsulated devices maintained 93% of the initial PCE after 1000 h in a humid and thermal environment (65 °C and 85% RH).
{"title":"Double-Chain Copolymer Network via In Situ Polymerization Enables High-Stability and Lead-Safe Perovskite Solar Cells","authors":"Jiaxin Ma, Shengnan Fan, Cong Shao, Lizhe Wang, Yuan Dong, Guosheng Niu, Zongxiu Nie, Shiyong Yang, Jizheng Wang, Haixia Yang","doi":"10.1002/anie.202425578","DOIUrl":"https://doi.org/10.1002/anie.202425578","url":null,"abstract":"Lead halide perovskite solar cells (PSCs) have made significant progress due to their low cost and high efficiency. However, the long-term stability and lead toxicity of PSCs remain a huge challenge for further commercialization. Herein, we designed a multifunctional additive PAE with photosensitive properties to overcome these difficulties. A unique double-chain copolymer network can be constructed via in situ polymerization induced by ultraviolet (UV) light. The multiple active sites in the polymer chains can passivate various defects and enhance charge transfer. Meanwhile, the vast network provides an effective defense for perovskite to stabilize the internal structure and resist harsh external environments, thus delaying the degradation of devices and maximizing the suppression of toxic lead leakage. Remarkably, the devices protected by the network achieved a champion power conversion efficiency (PCE) of 26.20% (certified as 25.69%), the unencapsulated devices suppressed 80% of lead leakage and the encapsulated devices maintained 93% of the initial PCE after 1000 h in a humid and thermal environment (65 °C and 85% RH).","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"56 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660754","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 we report a novel palladium/norbornene-catalyzed trifunctionalization reaction of ortho-unsubstituted iodoarenes by incorporating two distinct acyl groups at their ortho C-H positions and replacing the ipso-iodide with an alkenyl or aryl group. Notably, this transformation was enabled by the alkyl/aryl mixed anhydrides, which were utilized as dual acylation reagents by abstracting their central oxygen atom with electrophilic 2-chloro-4,6-dimethoxy-1,3,5-triazine. Mechanistic studies revealed that the alkyl-acyl unit of such an anhydride was employed for the first C-H alkyl-acylation, and in situ released aryl carboxylate anion was then rapidly activated with triazine chloride to provide an aryl-acyl electrophile for the second C-H acylation, thus enabling the trifunctionalization of iodoarenes by termination with an intermolecular Heck or intramolecular arylation reaction. In addition, the synthetic utility of this method is exemplified by the selective manipulation of carbonyl groups of the products.
{"title":"Trifunctionalization of Iodoarenes via Sequence-Controlled Double Ortho C-H Acylations by Palladium/Norbornene Catalysis","authors":"Yong Xu, Lifeng Wang, Aohua Yang, Jingyun Ren, Jingjing Liu, Xinjun Luan","doi":"10.1002/anie.202424604","DOIUrl":"https://doi.org/10.1002/anie.202424604","url":null,"abstract":"Herein we report a novel palladium/norbornene-catalyzed trifunctionalization reaction of ortho-unsubstituted iodoarenes by incorporating two distinct acyl groups at their ortho C-H positions and replacing the ipso-iodide with an alkenyl or aryl group. Notably, this transformation was enabled by the alkyl/aryl mixed anhydrides, which were utilized as dual acylation reagents by abstracting their central oxygen atom with electrophilic 2-chloro-4,6-dimethoxy-1,3,5-triazine. Mechanistic studies revealed that the alkyl-acyl unit of such an anhydride was employed for the first C-H alkyl-acylation, and in situ released aryl carboxylate anion was then rapidly activated with triazine chloride to provide an aryl-acyl electrophile for the second C-H acylation, thus enabling the trifunctionalization of iodoarenes by termination with an intermolecular Heck or intramolecular arylation reaction. In addition, the synthetic utility of this method is exemplified by the selective manipulation of carbonyl groups of the products.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"214 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660758","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 most exciting thing about my research is discovering a bizarre yet interesting phenomenon, and then spending several days to finally figure it out… If I were not a scientist, I would be a gardener, as I enjoy the process of nurturing seeds into beautiful flowers and experiencing the fulfillment of growth…”
{"title":"Yao-Yao Zhang","authors":"Yao-Yao Zhang","doi":"10.1002/anie.202504657","DOIUrl":"https://doi.org/10.1002/anie.202504657","url":null,"abstract":"<i>“The most exciting thing about my research is discovering a bizarre yet interesting phenomenon, and then spending several days to finally figure it out… If I were not a scientist, I would be a gardener, as I enjoy the process of nurturing seeds into beautiful flowers and experiencing the fulfillment of growth…”</i>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"90 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660707","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}
Sodium-ion batteries (SIBs) are emerging as a viable alternative for sustainable and cost-effective energy storage, yet their energy density is curtailed by relatively low voltage outputs (< 4 V) due to the lack of high-voltage electrolytes. Here, for the first time, we describe a high-voltage Na+ electrolyte featuring a macromolecule-enriched solvation architecture. The vulnerable small molecules in the Na+ solvation shell are replaced by macro polyamide (PA) molecules with high thermodynamic resilience, ensuring a wide electrochemical stability window for the electrolytes with suppressed oxidative/reductive decomposition. Concomitantly, the anions engage in H-bonding with the amido groups of PA, which not only stabilizes the anions against hydrolysis, but also delivers a high Na+ transference number of 0.93. Importantly, the nitrogen-rich composition of the macromolecule-enriched electrolyte (MEE) fosters the formation of robust nitride interphases that impart enduring stability to both the cathode and anode. As a result, the hard carbon (HC) || NaNi1/3Fe1/3Mn1/3O2 (NFM) full cells demonstrate significant rechargeability even with an ultrahigh cutoff voltage of 4.4 V. Our approach distinctively avoids the use of fluorinated molecules typically found in (localized-) high-concentration electrolytes, presenting a novel principle that could revolutionize high-voltage electrolyte design.
{"title":"Macromolecule-Enriched Solvation Enabling High-Voltage Sodium-Ion Batteries","authors":"Zhiming Zhao, Chen Liu, Tianxing Lai, Zehao Cui, Arumugam Manthiram","doi":"10.1002/anie.202423625","DOIUrl":"https://doi.org/10.1002/anie.202423625","url":null,"abstract":"Sodium-ion batteries (SIBs) are emerging as a viable alternative for sustainable and cost-effective energy storage, yet their energy density is curtailed by relatively low voltage outputs (< 4 V) due to the lack of high-voltage electrolytes. Here, for the first time, we describe a high-voltage Na+ electrolyte featuring a macromolecule-enriched solvation architecture. The vulnerable small molecules in the Na+ solvation shell are replaced by macro polyamide (PA) molecules with high thermodynamic resilience, ensuring a wide electrochemical stability window for the electrolytes with suppressed oxidative/reductive decomposition. Concomitantly, the anions engage in H-bonding with the amido groups of PA, which not only stabilizes the anions against hydrolysis, but also delivers a high Na+ transference number of 0.93. Importantly, the nitrogen-rich composition of the macromolecule-enriched electrolyte (MEE) fosters the formation of robust nitride interphases that impart enduring stability to both the cathode and anode. As a result, the hard carbon (HC) || NaNi1/3Fe1/3Mn1/3O2 (NFM) full cells demonstrate significant rechargeability even with an ultrahigh cutoff voltage of 4.4 V. Our approach distinctively avoids the use of fluorinated molecules typically found in (localized-) high-concentration electrolytes, presenting a novel principle that could revolutionize high-voltage electrolyte design.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"22 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666355","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 click chemist's playground: The most important certainty-of-chance outcome of click chemistry was the realization that perfect reactions can exist. Chemistry is about bond-making and bond-breaking reactions between atoms and molecules. So, the emergence of “perfect reaction” status promises to be transformative to the very heart of chemistry, and thence to the range of benefits for mankind that its future evolution may hold.
{"title":"Click Chemistry: The Certainty of Chance (Nobel Lecture)**","authors":"K. Barry Sharpless, M. G. Finn, Hartmuth C. Kolb","doi":"10.1002/anie.202501229","DOIUrl":"https://doi.org/10.1002/anie.202501229","url":null,"abstract":"The click chemist's playground: The most important certainty-of-chance outcome of click chemistry was the realization that perfect reactions can exist. Chemistry is about bond-making and bond-breaking reactions between atoms and molecules. So, the emergence of “perfect reaction” status promises to be transformative to the very heart of chemistry, and thence to the range of benefits for mankind that its future evolution may hold.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"34 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660706","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}
Christopher Mairhofer, Katharina Röser, Gabriel Burel, Sarah Merzinger, Jean-François Brière, Roland Obermüller, Mario Waser
We herein introduce a method for the direct a-amination of different carbonyl compounds by employing aqueous ammonia as the N-source. Upon using NH3 in combination with hypochlorites as simple oxidants under phase-transfer catalytic conditions it is possible to carry out the direct a-amination of reactive enolate-precursors such as cyclic b-ketoesters, oxindoles, as well as malonitriles and malonates with good to excellent yields, while simple ketone precursors being out of the scope thus far. Furthermore, a first proof-of-concept for an asymmetric variant by employing a chiral quaternary ammonium salt is reported.
{"title":"α-Amination of 1,3-Dicarbonyl Compounds and Analogous Reactive Enolate-Precursors Using Ammonia Under Oxidative Conditions","authors":"Christopher Mairhofer, Katharina Röser, Gabriel Burel, Sarah Merzinger, Jean-François Brière, Roland Obermüller, Mario Waser","doi":"10.1002/anie.202501586","DOIUrl":"https://doi.org/10.1002/anie.202501586","url":null,"abstract":"We herein introduce a method for the direct a-amination of different carbonyl compounds by employing aqueous ammonia as the N-source. Upon using NH3 in combination with hypochlorites as simple oxidants under phase-transfer catalytic conditions it is possible to carry out the direct a-amination of reactive enolate-precursors such as cyclic b-ketoesters, oxindoles, as well as malonitriles and malonates with good to excellent yields, while simple ketone precursors being out of the scope thus far. Furthermore, a first proof-of-concept for an asymmetric variant by employing a chiral quaternary ammonium salt is reported.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"56 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660708","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}
Shubham Vishnoi, Geetu Kumari, Robert Guest, Pierre-André Cazade, Sarah Guerin
Organic molecular crystals are ideally placed to become next-generation piezoelectric materials due to their diverse chemistries that can be used to engineer tailor-made solid-state assemblies. Using crystal engineering principles, and techniques such as co-crystallisation, these materials can be engineered to have a wide range of electromechanical properties. For materials that have been structurally characterised by methods such as X-Ray Diffraction, computational chemistry is an effective tool to predict their electromechanical properties, allowing researchers to screen these molecular crystals and identify materials best suited to their chosen application. Here we present our database of small molecular crystals, and their Density Functional Theory (DFT) predicted electromechanical properties, CrystalDFT (https://actuatelab.ie/CrystalDFT). We highlight the broad range of electromechanical properties amongst this primary dataset, and in particular, the high number of crystals that have a naturally occurring longitudinal piezoelectric response (d11/d22/d33). This longitudinal electromechanical coupling is a prerequisite for several conventional sensing and energy harvesting applications, the presence of which is notably rare amongst the literature on biomolecular crystal piezoelectricity to date.
{"title":"High-throughput computational screening of small, molecular crystals for sustainable piezoelectric materials","authors":"Shubham Vishnoi, Geetu Kumari, Robert Guest, Pierre-André Cazade, Sarah Guerin","doi":"10.1002/anie.202501232","DOIUrl":"https://doi.org/10.1002/anie.202501232","url":null,"abstract":"Organic molecular crystals are ideally placed to become next-generation piezoelectric materials due to their diverse chemistries that can be used to engineer tailor-made solid-state assemblies. Using crystal engineering principles, and techniques such as co-crystallisation, these materials can be engineered to have a wide range of electromechanical properties. For materials that have been structurally characterised by methods such as X-Ray Diffraction, computational chemistry is an effective tool to predict their electromechanical properties, allowing researchers to screen these molecular crystals and identify materials best suited to their chosen application. Here we present our database of small molecular crystals, and their Density Functional Theory (DFT) predicted electromechanical properties, CrystalDFT (https://actuatelab.ie/CrystalDFT). We highlight the broad range of electromechanical properties amongst this primary dataset, and in particular, the high number of crystals that have a naturally occurring longitudinal piezoelectric response (d11/d22/d33). This longitudinal electromechanical coupling is a prerequisite for several conventional sensing and energy harvesting applications, the presence of which is notably rare amongst the literature on biomolecular crystal piezoelectricity to date.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"26 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660755","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 utilization of carbon dioxide and alkenes as feedstocks for the synthesis of carboxylic acids holds great significance in the realm of sustainable chemistry. Nonetheless, achieving selective C−H bond carboxylation of alkenes with broad applicability has long been a challenging task. Herein, we present a straightforward and unifying approach for the preparation of α-carboxylic acids through nickel-catalyzed radical hydrocarboxylation of both functionalized and unactivated, simple alkenes, at proximal and remote sites. Notably, this operationally simple catalytic reaction exhibits a broad substrate scope, having excellent regio- and chemoselectivities, and is suitable for late-stage carboxylation of bioactive molecules. Preliminary mechanistic investigations showed that a nickel-catalyzed hydrogen atom transfer (Ni-HAT) pathway is in operation, accounting for the site-selective hydrocarboxylation protocol for various alkene substrates.
{"title":"Proximal and Remote Hydrocarboxylation of Alkenes with Carbon Dioxide Enabled by Nickel-Catalyzed Hydrogen Atom Transfer","authors":"Rong-De He, Yixin Lu","doi":"10.1002/anie.202424790","DOIUrl":"https://doi.org/10.1002/anie.202424790","url":null,"abstract":"The utilization of carbon dioxide and alkenes as feedstocks for the synthesis of carboxylic acids holds great significance in the realm of sustainable chemistry. Nonetheless, achieving selective C−H bond carboxylation of alkenes with broad applicability has long been a challenging task. Herein, we present a straightforward and unifying approach for the preparation of α-carboxylic acids through nickel-catalyzed radical hydrocarboxylation of both functionalized and unactivated, simple alkenes, at proximal and remote sites. Notably, this operationally simple catalytic reaction exhibits a broad substrate scope, having excellent regio- and chemoselectivities, and is suitable for late-stage carboxylation of bioactive molecules. Preliminary mechanistic investigations showed that a nickel-catalyzed hydrogen atom transfer (Ni-HAT) pathway is in operation, accounting for the site-selective hydrocarboxylation protocol for various alkene substrates.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"45 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660791","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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