Article
Chemistry, Multidisciplinary
Zhiqian Yu, Qianhui Liu, Qian Li, Zhenmei Huang, Yudong Yang, Jingsong You
Summary: In this study, we present a new approach allowing remote editing of stacked aromatic assemblies through the use of a transient ligand as a bridge. Our results demonstrate the successful heteroannular C-H functionalization and uncover a unique reaction mechanism involving olefin coordination.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Youliang He, Yuxiao Wang, Shi-Jun Li, Yu Lan, Xiaoming Wang
Summary: The cross-coupling of amides and polyfluoroarenes through direct C-H functionalization can lead to new carbon-carbon bond-forming methodologies, which have useful applications in synthesis, late-stage functionalization, and generation of molecular diversity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Chaolumen Bai, Bao Chao, Tegshi Muschin, Agula Bao, Menghe Baiyin, Dan Liu, Yong-Sheng Bao
Summary: This study reports the regioselective cross-coupling reactions in the o-methyl benzaldehyde frameworks using palladium catalysis, K2S2O8 or [F+] reagents as oxidants, and unactivated arenes as substrates/solvents. The regiospecificity is controlled by [5,6]-fused or [6,5]-fused palladacycle intermediates formed from Pd-chelation with specific transient directing groups and C-H activations.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Applied
Francisco Villalba, Ana C. Albeniz
Summary: The pyridone fragment in the ligand plays a crucial role in the C-H activation step of the oxidative Heck reaction. The presence of bipy-6-OH is required for the alkenylation of low acidity fluoroarenes, while it is detrimental for high acidity fluoroarenes. The use of catalytic amount of sodium molybdate as a base is optimal in all these reactions.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Princi Gupta, Suchithra Madhavan, Manmohan Kapur
Summary: In this study, a method for distal C-H functionalization of monosubstituted ferrocenes using an easily removable directing group under a Pd-II/ mono-N-protected amino-acid ligand catalytic system is reported. The synthetic protocol allows for the synthesis of ferrocene 1,3-derivatives with broad scope in olefins, by functionalizing ferrocenyl methylamine in moderate to good yields through a highly strained ferrocene appended 12-membered palladacycle intermediate.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Sif T. Linde, Vasco Corti, Vibeke H. Lauridsen, Johannes N. Lamhauge, Karl Anker Jorgensen, Nomaan M. Rezayee
Summary: This article presents a method for obtaining a versatile chiral biaryl structure through C-H halogenation reactions using high-valent Pd catalysis and chiral transient directing groups. The method is scalable, moisture and air insensitive, and in some cases, requires low Pd-loadings of only 1 mol%. Chiral mono-brominated, dibrominated, and bromochloro biaryls can be prepared in high yield and excellent stereoselectivity, serving as building blocks for various reactions with orthogonal synthetic handles.
Article
Chemistry, Multidisciplinary
Kananat Naksomboon, Enrique Gomez-Bengoa, Jaya Mehara, Jana Roithova, Edwin Otten, M. Angeles Fernandez-Ibanez
Summary: Pd-catalyzed C-H functionalization reactions of non-directed substrates have emerged as a promising alternative to the use of directing groups. A new type of S,O-ligand has been found to be highly efficient in promoting Pd-catalyzed C-H olefination reactions of non-directed arenes, although its role in the process was unclear. Through various mechanistic tools, it was discovered that C-H activation is the rate-determining step and the S,O-ligand triggers the formation of more reactive Pd cationic species, explaining the observed acceleration of the reaction. These findings provide important insights into the role of the S,O-ligand in promoting Pd-catalyzed C-H functionalization reactions.
Article
Chemistry, Organic
Chandrababu Naidu Kona, Yuji Nishii, Masahiro Miura
Summary: This report introduces a Rh-catalyzed C-7-selective alkenylation of indole derivatives using a new sulfur directing group N-SCy, which is easily installed to the indoles and removed after the catalysis under mild conditions.
Article
Chemistry, Multidisciplinary
Luo-Yan Liu, Zhoulong Fan, Md Emdadul Hoque, Shaoqun Qian, Guangrong Meng, Nikita Chekshin, Keita Tanaka, Jennifer X. X. Qiao, Kap-Sun Yeung, Jin-Quan Yu
Summary: Remote C-H functionalization of heterocyclic biaryls is crucial in synthesis and medicinal chemistry. New catalytic templates have been developed to functionalize the hindered ortho-C-H bonds of heterobiaryls, using directing heteroatom at the meta- or para-positions, with unprecedented site-selectivity. This protocol overcomes steric and electronic effects, allowing olefination of sterically hindered heterobiaryls.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Ka Yee Yee, Man Pan Leung, Man Ho Tse, Pui Ying Choy, Fuk Yee Kwong
Summary: This paper presents the first general examples of palladium-catalyzed direct C-H olefination of polyfluoroarenes using alkenyl tosylates as electrophilic coupling partners. Good-to-excellent yields of olefinated polyfluoroarenes can be obtained by employing the Pd/L1 catalyst system. The reaction exhibits good structural and functional compatibility, and particularly smooth reactivity for steric demanding and heterocyclic alkenyl tosylates. It can be practically performed on a gram-scale without significant loss of product yields.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Guoshuai Li, Yifei Yan, Pengfei Zhang, Xiaohua Xu, Zhong Jin
Summary: A new palladium-catalyzed meta-selective C-H olefination of aromatic carbonyl compounds was achieved by utilizing noncovalent hydrogen-bonding interaction directed by engineered N,N'-substituted ureas, demonstrating site-selective control without the need for prior stoichiometric installation and removal of directing groups.
Article
Chemistry, Applied
Suman Maji, Sukumar Pradhan, Karishma Pidiyara, Siddhartha Maiti, Shaeel A. Al-Thabaiti, Debabrata Maiti
Summary: This work presents a palladium(II)-catalyzed regioselective C8-H olefination of 1-naphthamides. Notably, naphthamide fused lactam 2,3-dihydro-1H-benzo[de]isoquinolin-1-one derivatives were synthesized in a particular class of napthamides. The reaction showed good compatibility with a diverse range of acrylates and styrenes, providing the desired products with high yields and tolerance to various functional groups. The developed strategy was further employed for the synthesis of different drug derivatives.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Martin Tomanik, Shaoqun Qian, Jin-Quan Yu
Summary: In this study, a novel reaction has been developed to convert carboxylic acids with olefin into bicyclo[3.2.1] lactone motifs. This reaction shows a broad substrate scope, excellent functional group compatibility, and can be extended to the synthesis of related lactone compounds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Applied
Takahiro Yamada, Kosaku Tanaka, Yoshimitsu Hashimoto, Nobuyoshi Morita, Osamu Tamura
Summary: Here, the authors describe a reaction system based on Pd(II) catalyst and Tl(OCOCF3)3 for the electrophilic C3-H alkenylation of 2,6-dialkoxypyridines with alkenes. The synergistic action of the Pd/thioether ligand catalytic system and Tl(III) enables efficient C-H alkenylation of various nitrogen heteroaromatics with complete regioselectivity. Mechanistic studies suggest that the reaction proceeds via electrophilic thallation of heteroarenes followed by Pd-catalyzed Heck-type reaction.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Liang Hu, Guangrong Meng, Jin-Quan Yu
Summary: This study reports the first Pd(II)-catalyzed intermolecular fi-methylene C(sp3)-H arylation of free aliphatic acids using bidentate pyridine-pyridone ligands. The bite angle of the ligand plays a key role in promoting fi-methylene C-H activation of free carboxylic acid. This transformation provides a disconnection for alkylation of arenes with simple aliphatic acids.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Shuai Liu, Yangen Huang, Juan Wang, Feng-Ling Qing, Xiu-Hua Xu
Summary: This study reports a method for the design and synthesis of novel N-Cbz- and N-Boc-N-trifluoromethyl hydroxylamine reagents using silver-mediated oxidative trifluoromethylation. These reagents have been successfully applied to incorporate a NCF3 moiety into commonly used unsaturated substrates, enabling efficient and regioselective C-H trifluoromethylamination. Additionally, a variety of substrates can undergo tandem trifluoromethylamination/functionalization to deliver structurally diverse N-trifluoromethyl aliphatic and heteroaromatic amines.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Dawei Zhang, Xing Gao, Qiao-Qiao Min, Yucheng Gu, Guillaume Berthon, Xingang Zhang
Summary: A nickel-catalyzed cross-coupling reaction of heteroaryl halides with chlorodifluoroacetamides and chlorodifluoroacetate has been developed, which offers an efficient and potential method for synthesizing medicinal compounds.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Yao-Yao Zhu, Shuai Liu, Yangen Huang, Feng-Ling Qing, Xiu-Hua Xu
Summary: The photoredox catalyzed difluoro(phenylthio)methylation of 2,3-allenoic acids with {difluoro(phenylthio)methyl}triphenylphosphonium triflate was investigated. A series of previously unknown 4-difluoro(phenylthio)methylated butenolides were synthesized through tandem radical difluoro(phenylthio)methylation/intramolecular cyclization.
JOURNAL OF FLUORINE CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Xiao-Tian Feng, Jin-Xiu Ren, Xing Gao, Qiao-Qiao Min, Xingang Zhang
Summary: We developed a new practical and stable difluoroalkylating reagent that can introduce the difluoromethylene group into organic molecules under mild reaction conditions via copper catalysis. The method exhibits high selectivity and efficiency and can be used for the synthesis of various complex analogs.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Minqi Zhou, Zhang Feng, Xingang Zhang
Summary: The site-selective modification of amino acids, peptides, and proteins has been an important topic in organic synthesis, medicinal chemistry, and chemical biology. The introduction of fluorine functionalities into these compounds has been a useful approach to alter their properties. Direct fluorination/fluoroalkylation of proteins has gained attention due to the unique properties of fluorine, and recent advances in the synthesis of fluorinated amino acids and peptides have been summarized in this article. Two strategies, based on fluorinated building blocks and direct fluorination/fluoroalkylation, have been discussed, providing powerful tools for selective access to fluorinated amino acids, peptides, and proteins.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Xin Zeng, Yao Li, Qiao-Qiao Min, Xiao-Song Xue, Xingang Zhang
Summary: The use of metal catalysts in controlling the reactivity of carbenes is widely used in organic synthesis, but the transfer of difluorocarbenes remains a challenge. In this study, isolable copper(I) difluorocarbene complexes were developed and used as catalysts for difluorocarbene transfer reactions. This strategy allows for the modular synthesis of organofluorine compounds and provides access to a variety of difluoromethylene-containing products. Mechanistic studies reveal a nucleophilic addition mechanism involving electrophilic copper(I) difluorocarbenes.
Article
Chemistry, Physical
Na Rao, Yun-Ze Li, Yun-Cheng Luo, Yanxia Zhang, Xingang Zhang
Summary: The nickel-catalyzed multicomponent dicarbofunctionalization of alkenes is a convenient method for synthesizing complex organofluorine compounds, but the catalytic carbofluoroalkylation of electron-deficient alkenes is still underdeveloped. In this study, a nickel-catalyzed three-component aryldifluoroalkylation reaction was reported, which involves the reaction of industry-relevant acrylonitrile and acrylate with arylboronic acids and difluoroalkyl halides. The reaction can be extended to a four-component nickel-catalyzed carbonylation reaction. This modular catalytic synthesis offers synthetic convenience, high functional group tolerance, and the ability to construct complex difluoroalkylated compounds efficiently. The utility of this synthesis has also been demonstrated by transforming the resulting products into fluorinated compounds of medicinal interest.
Article
Chemistry, Multidisciplinary
Yun-Cheng Luo, Ming-Kuan Wang, Ling-Chao Yu, Xingang Zhang
Summary: Here, we report a nickel-catalyzed selective C(sp(2))-F bond alkylation of HFO-1234yf with alkylzinc reagents, resulting in 2-trifluoromethylalkenes that can serve as versatile synthons for diversified transformations. Mechanistic studies reveal that the addition of lithium salt is crucial for promoting the oxidative addition of Ni-0(L-n) to the C-F bond, and less electron-rich N-based ligands exhibit comparable or higher oxidative addition rates compared to electron-rich phosphine ligands.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Xue-Ying Zhang, Shi-Ping Sun, Yue-Qian Sang, Xiao-Song Xue, Qiao-Qiao Min, Xingang Zhang
Summary: A palladium-catalyzed reductive difluorocarbene transfer reaction that utilizes chlorodifluoromethane as a precursor has been developed, allowing difluorocarbene to couple with two electrophiles. This new mode of difluorocarbene transfer reaction produces difluoromethylated (hetero)arenes from aryl halides/triflates and proton sources, with high functional group tolerance and synthetic convenience. Mechanistic studies reveal an unexpected Pd-0/II catalytic cycle involved in the reductive difluorocarbene transfer.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Xing Gao, Xiaoxiao Ren, Wei Deng, Xingang Zhang
Summary: This study reports a copper-catalyzed hydrodifluoroallylation of cyclopropenes and alkenyl boronates with 3,3-difluoroallyl sulfonium salts. The reaction shows high efficiency and stereoselectivity, allowing the synthesis of various gem-difluoroallyl cyclopropanes and borylalkanes under mild reaction conditions. The use of chiral phosphine ligand improves the enantioselectivity of the reaction. This method offers synthetic convenience, high functional group tolerance, and synthetic versatility of the resulting products.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Organic
Wenping Ding, Minqi Zhou, Huayu Li, Miao Li, Yanping Qiu, Yu Yin, Lifeng Pan, Wenchao Yang, Yanan Du, Xingang Zhang, Zhijun Tang, Wen Liu
Summary: Modification of organic molecules with fluorine functionalities is a critical approach for developing new pharmaceuticals. In this study, a multienzyme strategy for biocatalytic fluoroalkylation was reported, which involved the use of SAM-dependent methyltransferases and fluorinated SAM cofactors. The strategy demonstrated successful late-stage site-selective fluoroalkylation of the complex molecule vancomycin, with conversions up to 99%.
Article
Chemistry, Physical
Ming-Kuan Wang, Yun-Cheng Luo, Hai-Yang Zhao, Yanxia Zhang, Dawei Zhang, Xingang Zhang
Summary: A cobalt-catalyzed trans-selective arylfluoroalkylation of cyclopentenes has been developed for the efficient synthesis of polysubstituted cyclopentanes. The reaction exhibits broad substrate scope, high functional group tolerance, and synthetic convenience.
Article
Chemistry, Physical
Ling-Chao Yu, Yun-Cheng Luo, Wei Feng, Shu Zhang, Xingang Zhang
Summary: A new organic catholyte material, sodium 2-(4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl-4-yl)-2,2-difluoroacetate (DFTEMPO), is created by introducing a fluorine functionality into 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO), showing higher cell voltage, rate capability, and cycle stability in aqueous redox flow batteries (ARFBs).
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Chemistry, Multidisciplinary
Hao-Wen Li, Yun-Cheng Luo, Ling-Chao Yu, Xingang Zhang
Summary: A palladium-catalyzed gem-difluoroallylation of propargyl sulfonates with gem-difluoroallylboron has been developed, providing a synthetic route to 3,3-difluoro-skipped 1,5-enynes with high efficiency and regioselectivity. The resulting products can serve as versatile synthons for diversified transformations and have potential applications in medicinal chemistry.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Xiaoxiao Ren, Xing Gao, Qiao-Qiao Min, Shu Zhang, Xingang Zhang
Summary: This research reports a novel method for constructing the alkylCF(2)-alkyl bond using alkylzirconocene as a catalyst to promote the reaction between unactivated difluoroalkyl iodides and bromides and alkyl- and silyl-alkenes under visible light irradiation without a catalyst. The resulting difluoroalkylated compounds can serve as versatile synthons in organic synthesis, and the reaction can also be applied to other fluorinated compounds.
Article
Chemistry, Organic
Geeta Devi Yadav, Pooja Chaudhary, Balaram Pani, Surendra Singh
Summary: Chiral transition metal complexes with privileged ligands are efficient catalysts for various asymmetric organic transformations. Transition metal complexes of C1-symmetric pyrrolidine-based ligands have been widely used in asymmetric organic reactions. However, a comprehensive review article on the transition metal complexes of chiral C1-symmetric pyrrolidine-based ligands derived from (L)-proline has not been published.
TETRAHEDRON LETTERS
(2024)
