We developed a new type of catalytic arylative cyclization of 1,6-enynes, whereby an aryl group is introduced at an unactivated alkene moiety rather than at an alkyne moiety. The reaction of a 1,6-enyne with an arylboronic acid in the presence of an Ni(cod)2/P(4-MeOC6H4)3 complex yields a five-membered ring product incorporating an all-carbon quaternary center. Experimental studies and extensive DFT calculations reveal that an Ni(I) species is involved in the catalytic cycle, which is an uncommon pathway involving transmetalation, cycloisomerization, selective sp3–sp2 carbon–carbon bond formation, and finally hydrolysis.
{"title":"Nickel-catalyzed arylative cyclization of 1,6-enynes: arylation of unactivated alkene moieties","authors":"Jian Gao, Qi Wei, Zeqing Zhang, Zhishan Su, Jialin Ming, Yongmin Zhang","doi":"10.1039/d4qo00784k","DOIUrl":"https://doi.org/10.1039/d4qo00784k","url":null,"abstract":"We developed a new type of catalytic arylative cyclization of 1,6-enynes, whereby an aryl group is introduced at an unactivated alkene moiety rather than at an alkyne moiety. The reaction of a 1,6-enyne with an arylboronic acid in the presence of an Ni(cod)<small><sub>2</sub></small>/P(4-MeOC<small><sub>6</sub></small>H<small><sub>4</sub></small>)<small><sub>3</sub></small> complex yields a five-membered ring product incorporating an all-carbon quaternary center. Experimental studies and extensive DFT calculations reveal that an Ni(I) species is involved in the catalytic cycle, which is an uncommon pathway involving transmetalation, cycloisomerization, selective sp3–sp2 carbon–carbon bond formation, and finally hydrolysis.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141452930","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 series of pentafluoroethylation reactions of styrene derivatives are described using the [CuCF2CF3] reagent prepared from low-cost pentafluoroethane (HCF2CF3). Under aerobic conditions, chloropentafluoroethylation, dimerization-pentafluoroethylation, vinylic pentafluoroethylation, formyloxylation-pentafluoroethylation and hydroxypentafluoroethylation can be achieved using styrenes to generate various functionalized products containing the CF2CF3 group. It is remarkable a single reagent is capable of such divergent reactivities with readily available feedstocks.
{"title":"Divergent Pentafluoroethylation of Styrene Derivatives Using CuCF2CF3","authors":"Gavin Chit Tsui, Zhengjie Fu","doi":"10.1039/d4qo00768a","DOIUrl":"https://doi.org/10.1039/d4qo00768a","url":null,"abstract":"A series of pentafluoroethylation reactions of styrene derivatives are described using the [CuCF2CF3] reagent prepared from low-cost pentafluoroethane (HCF2CF3). Under aerobic conditions, chloropentafluoroethylation, dimerization-pentafluoroethylation, vinylic pentafluoroethylation, formyloxylation-pentafluoroethylation and hydroxypentafluoroethylation can be achieved using styrenes to generate various functionalized products containing the CF2CF3 group. It is remarkable a single reagent is capable of such divergent reactivities with readily available feedstocks.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141453145","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}
Density functional theory (DFT) calculations reveal a distinct mechanism for the Au(I)-catalyzed synthesis of bicyclo-[2.2.1]heptanes through cycloisomerizations of 3-alkoxyl-1,6-diynes. The proposed mechanism highlights the crucial involvement of an allyl-gold species and rationalizes all experimental observations, including the solvent-controlled chemodivergence of the reaction. Specifically, in the less polar toluene solvent, the reaction involves a key allyl-gold species with an energy barrier of 24.1 kcal mol-1, leading to the bridged ring product. Conversely, in the polar 1,2-dichloroethane solvent, the reaction occurs via an alkyl-gold species with an energy barrier of 29.2 kcal mol-1, delivering the monocyclic product. This new reactivity concept could potentially assist the exploration of new and unconventional strategies for the preparation of bridged ring systems.
{"title":"Insights into the Mechanism and Origin of Solvent-Controlled Chemodivergence in the Synthesis of Au-Catalyzed Bicyclo[2.2.1]heptanes from 3-Alkoxy-1,6-Diynes: A DFT Perspective","authors":"Aili Feng, Dongju Zhang","doi":"10.1039/d4qo00816b","DOIUrl":"https://doi.org/10.1039/d4qo00816b","url":null,"abstract":"Density functional theory (DFT) calculations reveal a distinct mechanism for the Au(I)-catalyzed synthesis of bicyclo-[2.2.1]heptanes through cycloisomerizations of 3-alkoxyl-1,6-diynes. The proposed mechanism highlights the crucial involvement of an allyl-gold species and rationalizes all experimental observations, including the solvent-controlled chemodivergence of the reaction. Specifically, in the less polar toluene solvent, the reaction involves a key allyl-gold species with an energy barrier of 24.1 kcal mol-1, leading to the bridged ring product. Conversely, in the polar 1,2-dichloroethane solvent, the reaction occurs via an alkyl-gold species with an energy barrier of 29.2 kcal mol-1, delivering the monocyclic product. This new reactivity concept could potentially assist the exploration of new and unconventional strategies for the preparation of bridged ring systems.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141452824","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A novel strategy for the construction of polysubstituted pyrroles has been developed through visible-light induced single-electron reduction of CAr-I bonds and the following 1,5-hydrogen atom transfer (HAT) process. This protocol facilities the smooth reactions between cyclic 2-iodobenzoyl amides and internal alkynes bearing electron-withdrawing groups (EWGs), affording a wide range of pyrrole skeletons with diverse substitution patterns. Preliminary mechanistic explorations along with density functional theory (DFT) calculations indicate that the 1,5-HAT process triggered by CAr-I activation is crucial to the successful transformation. Scale-up reaction and late-stage modification of natural products further highlight the synthetic potential of this method.
{"title":"Visible-light-mediated synthesis of polysubstituted pyrroles via CAr-I reduction triggered 1,5-hydrogen atom transfer process","authors":"Junlei Wang, Qinglin Xie, Guocheng Gao, Guofen Wei, Xinxin Wei, Xuemei Chen, Daohai Zhang, Hongqing Li, Binbin Huang","doi":"10.1039/d4qo00953c","DOIUrl":"https://doi.org/10.1039/d4qo00953c","url":null,"abstract":"A novel strategy for the construction of polysubstituted pyrroles has been developed through visible-light induced single-electron reduction of CAr-I bonds and the following 1,5-hydrogen atom transfer (HAT) process. This protocol facilities the smooth reactions between cyclic 2-iodobenzoyl amides and internal alkynes bearing electron-withdrawing groups (EWGs), affording a wide range of pyrrole skeletons with diverse substitution patterns. Preliminary mechanistic explorations along with density functional theory (DFT) calculations indicate that the 1,5-HAT process triggered by CAr-I activation is crucial to the successful transformation. Scale-up reaction and late-stage modification of natural products further highlight the synthetic potential of this method.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141452811","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}
Huajun Zhang, Aoxin Guo, Han Ding, Yuan Xu, Yuhan Zhang, Dan Yang, Xue-Wei Liu
Herein, we report an efficient, stereoselective synthesis of 2,3-unsaturated glycosides under mild conditions through a novel Ferrier rearrangement of reasonably designed glycal donors with C3-position ortho-2,2-dimethoxycarbonycyclopropylbenzoyl (CCBz), facilitated by user-friendly, eco- and environmental-friendly Cu(OTf)2 or Fe(OTf)3. The newly devised rearrangement tactic is highly α-stereoselective and applies to a broad scope of nucleophile acceptors, enabling the construction of 2,3-unsaturated O-, S-, N-, and C-glycosides, with exceptional yields and stereoselectivities. DFT calculations were conducted to elucidate the reaction mechanism, unveiling the dual role of the metal catalysts in activating the glycal donor through promoting ring-opening of the intramolecularly incorporated donor–acceptor cyclopropane (DAC) of CCBz and directing the following α-face-preferential nucleophilic attack of the incoming acceptor mediated by H-bond interactions.
{"title":"Stereoselective strain-release Ferrier rearrangement: the dual role of catalysts","authors":"Huajun Zhang, Aoxin Guo, Han Ding, Yuan Xu, Yuhan Zhang, Dan Yang, Xue-Wei Liu","doi":"10.1039/d4qo00410h","DOIUrl":"https://doi.org/10.1039/d4qo00410h","url":null,"abstract":"Herein, we report an efficient, stereoselective synthesis of 2,3-unsaturated glycosides under mild conditions through a novel Ferrier rearrangement of reasonably designed glycal donors with C3-position <em>ortho</em>-2,2-dimethoxycarbonycyclopropylbenzoyl (CCBz), facilitated by user-friendly, eco- and environmental-friendly Cu(OTf)<small><sub>2</sub></small> or Fe(OTf)<small><sub>3</sub></small>. The newly devised rearrangement tactic is highly α-stereoselective and applies to a broad scope of nucleophile acceptors, enabling the construction of 2,3-unsaturated <em>O</em>-, <em>S</em>-, <em>N</em>-, and <em>C</em>-glycosides, with exceptional yields and stereoselectivities. DFT calculations were conducted to elucidate the reaction mechanism, unveiling the dual role of the metal catalysts in activating the glycal donor through promoting ring-opening of the intramolecularly incorporated donor–acceptor cyclopropane (DAC) of CCBz and directing the following α-face-preferential nucleophilic attack of the incoming acceptor mediated by H-bond interactions.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141453103","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}
Huan Zhang, Zhonghe Cui, Jian Wang, Lin Zhu, Chao-Zhong Li
Here an unprecedented formal deformylative phosphonylation is disclosed. Under the catalysis of 1 mol % 1,2,3,5-tetrakis(diphenylamino)-4,6-dicyanobenzene (4DPAIPN) and the presence of 200 mol % triethylamine as additive, 4-alkyl-1,4-dihydropyridines (DHPs), derived from aldehydes, underwent phosphonylation smoothly with 9-fluorenyl o-phenylene phosphite, allowing facile synthesis of alkylphosphonates. This strategy is applicable to primary, secondary, and even tertiary DHPs, and exhibits a broad substrate scope and excellent functional group tolerance, thereby enabling the late-stage phosphonylation of a series of naturally-ocurring bioactive and biorelevant molecules.
{"title":"Facile Synthesis of Alkylphosphonates from 4-Alkyl-1,4-Dihydropyridines via Photoinduced Formal Deformylative Phosphonylation","authors":"Huan Zhang, Zhonghe Cui, Jian Wang, Lin Zhu, Chao-Zhong Li","doi":"10.1039/d4qo00863d","DOIUrl":"https://doi.org/10.1039/d4qo00863d","url":null,"abstract":"Here an unprecedented formal deformylative phosphonylation is disclosed. Under the catalysis of 1 mol % 1,2,3,5-tetrakis(diphenylamino)-4,6-dicyanobenzene (4DPAIPN) and the presence of 200 mol % triethylamine as additive, 4-alkyl-1,4-dihydropyridines (DHPs), derived from aldehydes, underwent phosphonylation smoothly with 9-fluorenyl o-phenylene phosphite, allowing facile synthesis of alkylphosphonates. This strategy is applicable to primary, secondary, and even tertiary DHPs, and exhibits a broad substrate scope and excellent functional group tolerance, thereby enabling the late-stage phosphonylation of a series of naturally-ocurring bioactive and biorelevant molecules.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141452812","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}
Despite extensive efforts in metal-free synthesis, strained cyclic diacyl peroxides have not been invoked as external oxidants in high-oxidation-state palladium-catalyzed reactions and their involvements in corresponding elementary steps were not studied. Herein, a PdII-catalyzed intramolecular oxidative C‒H amination has been successfully developed for the construction of carbazole architectures under additive-free and mild conditions. The presented method proved to be compatible with a variety of functional groups and scalable synthesis, which enabled the late-stage diversification of bioactive molecules as well as facilitated concise syntheses of carbazole alkaloid derivatives. Importantly, the use of strained cyclic diacyl peroxides as a sacrificial oxidant is critical for controlling the reactivity of high-valent Pd intermediates and the selectivity to multiple competing reductive elimination events, owing to the rigid constraint imposed by the bidentate dicarboxylate ligand. Mechanistic studies suggested that this reaction proceeds via a unique PdII/PdIV manifold, and the turnover-limiting step is substrate coordination to palladium catalyst. Moreover, photophysical investigation showed that varying N-protecting groups and increasing conjugated systems had a clear influence on the photophysical properties of carbazole derivatives. The calculation of six green metrics demonstrates the latent greenness of this catalytic system.
尽管在无金属合成方面做出了大量努力，但在高氧化态钯催化反应中，应变环二酰基过氧化物尚未被用作外部氧化剂，它们在相应基本步骤中的参与也未被研究。在此，我们成功开发了一种 PdII 催化的分子内氧化 C-H 氨基化反应，用于在无添加剂和温和的条件下构建咔唑结构。事实证明，该方法兼容多种官能团并可进行规模化合成，从而实现了生物活性分子的后期多样化，并促进了咔唑生物碱衍生物的简便合成。重要的是，由于双齿二羧酸配体的刚性约束，使用受约束的环状二酰过氧化物作为牺牲氧化剂对于控制高价钯中间体的反应性和对多种竞争还原消除事件的选择性至关重要。机理研究表明，该反应是通过独特的 PdII/PdIV 流形进行的，周转限制步骤是底物与钯催化剂的配位。此外，光物理研究表明，不同的 N 保护基团和共轭体系的增加对咔唑衍生物的光物理特性有明显的影响。六项绿色指标的计算表明了该催化系统潜在的绿色性。
{"title":"Palladium(II)-catalyzed intramolecular C−H amination to carbazole: crucial role of cyclic diacyl peroxides","authors":"Ting Yuan, Kang Fu, Lei Shi","doi":"10.1039/d4qo00779d","DOIUrl":"https://doi.org/10.1039/d4qo00779d","url":null,"abstract":"Despite extensive efforts in metal-free synthesis, strained cyclic diacyl peroxides have not been invoked as external oxidants in high-oxidation-state palladium-catalyzed reactions and their involvements in corresponding elementary steps were not studied. Herein, a PdII-catalyzed intramolecular oxidative C‒H amination has been successfully developed for the construction of carbazole architectures under additive-free and mild conditions. The presented method proved to be compatible with a variety of functional groups and scalable synthesis, which enabled the late-stage diversification of bioactive molecules as well as facilitated concise syntheses of carbazole alkaloid derivatives. Importantly, the use of strained cyclic diacyl peroxides as a sacrificial oxidant is critical for controlling the reactivity of high-valent Pd intermediates and the selectivity to multiple competing reductive elimination events, owing to the rigid constraint imposed by the bidentate dicarboxylate ligand. Mechanistic studies suggested that this reaction proceeds via a unique PdII/PdIV manifold, and the turnover-limiting step is substrate coordination to palladium catalyst. Moreover, photophysical investigation showed that varying N-protecting groups and increasing conjugated systems had a clear influence on the photophysical properties of carbazole derivatives. The calculation of six green metrics demonstrates the latent greenness of this catalytic system.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141453138","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 stereo-selective preparation of multi-substituted dienes and eneynes by sequential hydroarylation of internal alkynes via five-membered rhodacycle and olefinic C–H functionalization, including alkenylation, alkynylation and allylation through seven-membered endo-cyclopalladation, both enabled by the N,N-bidentate chelation assistance of pyrazinamide or picolinamide. The robustness and generality of the protocol have been demonstrated by the smooth conversion of a wide range of benzyl amides to afford up to 92% yields with E/Z ratio selectivity up to >99/1, as well as a successful gram-scaled synthesis. Further chemical derivations and photophysical properties of products were also examined.
{"title":"Stereo-selective synthesis of complex dienes and eneynes by sequential hydroarylation and olefinic C–H functionalization","authors":"Yuhang Zhu, Xiaoli Li, Cheng Zhang, Xiuying Liu, Linzhi Huang, Yongbo Zhang, Chao Shen, Liyuan Ding, Guofu Zhong, Jian Zhang","doi":"10.1039/d4qo00726c","DOIUrl":"https://doi.org/10.1039/d4qo00726c","url":null,"abstract":"We present a stereo-selective preparation of multi-substituted dienes and eneynes by sequential hydroarylation of internal alkynes <em>via</em> five-membered rhodacycle and olefinic C–H functionalization, including alkenylation, alkynylation and allylation through seven-membered <em>endo</em>-cyclopalladation, both enabled by the <em>N</em>,<em>N</em>-bidentate chelation assistance of pyrazinamide or picolinamide. The robustness and generality of the protocol have been demonstrated by the smooth conversion of a wide range of benzyl amides to afford up to 92% yields with <em>E</em>/<em>Z</em> ratio selectivity up to >99/1, as well as a successful gram-scaled synthesis. Further chemical derivations and photophysical properties of products were also examined.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141444833","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 highly selective photocatalytic deuterodefluorination of fluorinated esters with D2O is presented. By tailoring the catalytic system, a variety of α,α-difluoroaryl acetates underwent selective defluorination/deuteration to afford the 2-fluoro-2-arylacetate-d and 2-arylacetate-d2 in good yields with excellent deuteration rate. Satisfactorily, this protocol was successfully applied to deuterate some drug molecules, such as the felbinacethyl-d2 and felbilnac-d2.
{"title":"Photoredox-Catalyzed Selective Deuterodefluorination of α, α-Difluoroarylacetic Esters and Amides","authors":"Li-Na Guo, Xin-Hua Duan, Zi-Hang Yuan, Yuan Gao, Hong Xin, Guowei Sun, Ruiying Zhao","doi":"10.1039/d4qo00781f","DOIUrl":"https://doi.org/10.1039/d4qo00781f","url":null,"abstract":"A highly selective photocatalytic deuterodefluorination of fluorinated esters with D2O is presented. By tailoring the catalytic system, a variety of α,α-difluoroaryl acetates underwent selective defluorination/deuteration to afford the 2-fluoro-2-arylacetate-d and 2-arylacetate-d2 in good yields with excellent deuteration rate. Satisfactorily, this protocol was successfully applied to deuterate some drug molecules, such as the felbinacethyl-d2 and felbilnac-d2.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-06-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141439854","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 direct synthesis of novel gold(III)-annulated perylene diimides (Au-PDIs and Au2-PDIs) from ortho-pyridyl-substituted PDIs, achieving facile auration of two or four C-H bonds in one pot. Au2-PDI 12 (λmax = 635 nm) emerged as the most red-shifted compound among all reported heteroannulated PDIs. Cyclic voltammetry and density functional theory calculations indicate degenerated LUMO levels and substantial narrowing of HOMO-LUMO energy gaps. This synthetic strategy is expected to unlock the potential of diverse transition metal-annulated PDIs.
{"title":"Direct Synthesis of Gold(III)-Annulated Perylene Diimides via Multiple C-H Auration","authors":"Wei Chen, Qingyu Yang, Kongchuan Wu, Jianbin Lin, Hui-Jun Zhang","doi":"10.1039/d4qo01075b","DOIUrl":"https://doi.org/10.1039/d4qo01075b","url":null,"abstract":"We present a direct synthesis of novel gold(III)-annulated perylene diimides (Au-PDIs and Au2-PDIs) from ortho-pyridyl-substituted PDIs, achieving facile auration of two or four C-H bonds in one pot. Au2-PDI 12 (λmax = 635 nm) emerged as the most red-shifted compound among all reported heteroannulated PDIs. Cyclic voltammetry and density functional theory calculations indicate degenerated LUMO levels and substantial narrowing of HOMO-LUMO energy gaps. This synthetic strategy is expected to unlock the potential of diverse transition metal-annulated PDIs.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":5.4,"publicationDate":"2024-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141435977","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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