Article
Chemistry, Multidisciplinary
Daigo Hayashi, Tomohiro Tsuda, Ryo Shintani
Summary: A palladium-catalyzed skeletal rearrangement has been developed to synthesize highly fused tetrahydrophenanthrosilole derivatives via bond exchange. The reaction conditions can be tuned to produce different products, fused dihydrodibenzosilepin derivatives.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Qikai Sun, Huixing Zhang, Quanquan Wang, Tianjiao Qiao, Gang He, Gong Chen
Summary: A new strategy has been developed for the stereoselective synthesis of C-vinyl glycosides, using Pd-catalyzed directed C-H glycosylation. This method offers a broadly applicable approach to streamline the synthesis of complex C-vinyl glycosides with high efficiency and excellent regio- and stereoselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
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, Physical
Seo Jin Yun, Jisu Kim, Eunsu Kang, Hoimin Jung, Hyun Tae Kim, Minkyu Kim, Jung Min Joo
Summary: The development of ligands and their roles in the catalytic cycle are crucial for achieving high efficiency and selectivity in nondirected transition-metal-catalyzed C-H functionalization. In this study, pyrazolopyridone (PzPyOH) ligands were developed for Pd-catalyzed perdeuteration and meta-selective alkenylation. The ligands facilitated C-H cleavage and enabled perdeuteration due to the incorporation of the 2-pyridone moiety, and the ligand properties allowed for selective functionalization of meta-positions in alkenylation.
Article
Chemistry, Physical
Seo Jin Yun, Jisu Kim, Eunsu Kang, Hoimin Jung, Hyun Tae Kim, Minkyu Kim, Jung Min Joo
Summary: The development of ligands and their role in catalytic cycles are essential for achieving high efficiency and selectivity in non-directed transition metal catalyzed C-H functionalization. In this study, a series of pyrazolopyridone (PzPyOH) ligands were designed for Pd-catalyzed perdeuteration and meta-selective alkenylation of arenes. The ligands incorporate a 2-pyridone moiety as an internal base, allowing for reversible C-H activation and enabling perdeuteration. The ligands also exhibit flexibility in binding to Pd, facilitating coordination with alkene coupling partners during alkenylation.
Article
Chemistry, Organic
Xia-xin Sheng, Yu-jia Du, Jun-hua Li, Qiao-qiao Teng, Ming Chen
Summary: This article describes a palladium-catalyzed photoinduced N-to-alkyl radical relay Heck reaction, where o-alkylbenzamides at benzylic sites are reacted with vinyl arenes. The reaction does not require exogenous photosensitizers or external oxidants, and is proposed to proceed via a N-to-alkyl hybrid palladium-radical mechanism. The reaction occurs under mild conditions, allowing a wide range of functional groups to be compatible. The products can be easily transformed into azepinone derivatives, which are commonly found in pharmaceuticals and natural products.
Article
Chemistry, Organic
Xun-Shen Liu, Mingjia Li, Kexin Dong, Shaoting Peng, Lu Liu
Summary: In this paper, a highly stereoselective Rh(II)-catalyzed 1,4-acyl rearrangement of selenium esters and alpha-diazo carbonyl compounds is disclosed, which provides an efficient method for synthesizing tetrasubstituted vinyl selenides. Furthermore, this reaction also offers a synthetic tool for medium and large ring compounds.
Article
Chemistry, Multidisciplinary
Hai-Yun Huang, Amal Benzai, Xinzhe Shi, Henri Doucet
Summary: Researchers are focused on developing different procedures for direct functionalization of two different C-H bonds of the same organic molecule, which is currently an important research topic in organic chemistry. Over the past decade, the number of tools to control regiodivergent C-H bond functionalizations has significantly increased.
Article
Chemistry, Multidisciplinary
Xiaolan Xin, Yilin Liu, Lu Zhou, You Li, Han Luo, Lei Liu, Ruopeng Bai, Yu Lan, Baosheng Li
Summary: In this study, a Pd-catalyzed regiospecific cycloaromatization of beta-bromoenal and vinyl borate esters is reported to synthesize m-alkenyl substituted benzaldehydes. This method allows the construction of complex molecules from simple materials and may be valuable in the search for new optical materials.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Shanmugarajan Jothi Murugan, Masilamani Jeganmohan
Summary: An efficient and straightforward strategy for the synthesis of isoquinolones through [4 + 2]-annulation was described. Through utilizing N-chlorobenzamides and vinyl acetate, isoquinolone derivatives were prepared in good yields with the presence of CoCp*(III) catalyst in a regioselective manner. Furthermore, the annulation reaction was diversified by using vinyl ketones. Mechanistic investigations such as deuterium labeling study and competition experiment were performed to support the proposed reaction mechanism.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Shanmugarajan Jothi Murugan, Masilamani Jeganmohan
Summary: This study describes an efficient and regioselective synthesis of isoquinolones by [4 + 2]-annulation of N-chlorobenzamides with vinyl acetate in the presence of CoCp*(III) catalyst. The annulation reaction was further diversified by using vinyl ketones, leading to the preparation of biologically valuable isoquinolone derivatives in good yields. Additionally, mechanistic investigations including deuterium labeling study and competition experiment were performed to support the proposed reaction mechanism.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Fangzhi Hu, Zhipeng Sun, Mengzhe Pan, Liang Wang, Lubin Xu, Xiong-Li Liu, Shuai-Shuai Li
Summary: A H2O-promoted controllable synthesis of diverse nitrogen heterocycles was developed using a hydride transfer strategy. Various 3-carboxyl and 3-acyl substituted tetrahydroquinolines and 3,4-dihydroquinolin-2(1H)-ones were obtained via cascade reactions. The methodology's synthetic utility and mechanistic studies were also presented.
Article
Chemistry, Multidisciplinary
Anna Skrzynska, Sebastian Frankowski, Aleksandra Topolska, Mateusz Dyguda, Xin-Yue Gao, Chang-Jiang Xu, Ying-Chun Chen, Lukasz Albrecht
Summary: In this work, a novel H-bond-directed vinylogous iminium ion strategy has been developed for the gamma, delta-functionalization of vinyl-substituted heteroaromatic aldehydes. The strategy allows for the synthesis of tricyclic compounds with excellent stereoselectivity, demonstrating the potential applications in complex molecule synthesis.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Fabio Julia, Jiyao Yan, Fritz Paulus, Tobias Ritter
Summary: A vinyl thianthrenium salt has been introduced as an effective vinylating reagent, which can be readily prepared from ethylene gas and is broadly useful in various annulation chemistry reactions. Its unique structural features enable a distinct synthesis and reactivity profile, unprecedented for other vinyl sulfonium derivatives.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Multidisciplinary Sciences
Daniel A. Strassfeld, Chia-Yu Chen, Han Seul Park, D. Quang Phan, Jin-Quan Yu
Summary: The functionalization of C-H bonds in organic molecules is a direct approach for chemical synthesis. Recent advances in catalysis have allowed various chemical groups to control and direct C(sp(3))-H activation, but alcohols, a common functionality, have remained difficult to react due to their low affinity for catalysts. This study describes ligands that enable alcohol-directed arylation of C(sp(3))-H bonds through charge balance and hydrogen-bonding interactions, thus enhancing substrate-catalyst affinity and enabling previously unknown reactivity.
Article
Chemistry, Organic
Lin Qiu, Hao Jiang, Yanbo Yu, Jiwei Gu, Jinzhi Wang, Haiyang Zhao, Tianyu Huang, Robert J. Gropler, Robyn S. Klein, Joel S. Perlmutter, Zhude Tu
Summary: The study has developed a new multiple step F-18 labeling strategy, successfully synthesized the [F-18]FS1P1 radiotracer with the same structure as the existing tracer [C-11]CS1P1. The radiotracer showed high metabolic stability and effective method for detecting neuroinflammatory status in animal models.
ORGANIC & BIOMOLECULAR CHEMISTRY
(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
Radiology, Nuclear Medicine & Medical Imaging
Yanbo Yu, Hao Jiang, Qianwa Liang, Lin Qiu, Tianyu Huang, Hongzhen Hu, Vadim Y. Bolshakov, Joel S. Perlmutter, Zhude Tu
Summary: In this study, a new C-11 radiotracer [C-11]HC070 was synthesized and evaluated for imaging TRPC5 in rodents and nonhuman primates. The results showed that [C-11]HC070 has high brain uptake and good brain washout pharmacokinetics.
MOLECULAR IMAGING AND BIOLOGY
(2023)
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)
Article
Multidisciplinary Sciences
Yun-Ze Li, Na Rao, Lun An, Xiao-Long Wan, Yanxia Zhang, Xingang Zhang
Summary: The authors report a nickel-catalyzed enantioselective dicarbofunctionalization reaction of 3,3,3-trifluoropropene, which overcomes side reactions and provides a convenient method for the synthesis of chiral trifluoromethylated compounds.
NATURE COMMUNICATIONS
(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)