Article
Chemistry, Multidisciplinary
Jiandong Liu, Hegui Gong, Shaolin Zhu
Summary: A NiH-catalyzed migratory hydroalkenylation reaction of olefins with alkenyl bromides has been developed, yielding benzylic alkenylation products with high yields and excellent chemoselectivity. The mild conditions of the reaction prevent olefinic products from further isomerization or subsequent alkenylation, and catalytic enantioselective hydroalkenylation of styrenes was achieved using a chiral bisoxazoline ligand.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Yu-Qi Miao, Qiao-Jing Pan, Zhenxing Liu, Xuenian Chen
Summary: A green and practical photoinduced method for regioselective hydroboration of electron-deficient alkenes has been developed using 1,2-diphenyldisulfane as a photocatalyst and HAT reagent precursor. This mild protocol allows for the synthesis of various borylated compounds under excellent selectivity and functional group tolerance.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Physical
Nahiane Pipaon Fernandez, Gregory Gaube, Kyla J. Woelk, Mathias Burns, Damian P. Hruszkewycz, David C. Leitch
Summary: We present a new method for direct C-C bond formation using tandem C-O/C-H activation mediated by palladium catalyst. This approach allows for base-free direct C-H alkenylation by combining C-O oxidative addition at enol pivalates and concerted metalation-deprotonation of functionalized heterocycles. Mechanistic studies show that C-O oxidative addition is reversible and C-H activation occurs directly from the Pd(II) C-O oxidative addition product. In situ P-31 NMR spectroscopy reveals that (Cy3P)(2)Pd-(alkenyl)(OPiv) species is the predominant catalyst resting state during the reactions.
Article
Chemistry, Organic
Hideo Setsumasa, Kosuke Imai, Ikumi Kobayashi, Masahisa Nakada
Summary: This study describes the Pd-catalyzed stereoselective synthesis of decalins with one-carbon units bearing heteroatoms at the ring junction. The Pd-catalyzed cyclization of silyl enol ether resulted in the exclusive formation of the cis isomer (89%, >100/1 cis/trans). Conversely, Pd-catalyzed carboiodination and carboborylation reactions (with oxidative workup) provided products with yields of 56% (1/>100 cis/trans) and 69% (1/11 cis/trans), respectively.
Article
Chemistry, Organic
Hideo Setsumasa, Kosuke Imai, Ikumi Kobayashi, Masahisa Nakada
Summary: The Pd-catalyzed stereoselective construction of decalins with one-carbon units bearing heteroatoms at the ring junction is described. The Pd-catalyzed cyclization of silyl enol ether resulted in exclusive formation of the cis isomer (89%, >100/1 cis/trans). On the contrary, Pd-catalyzed carboiodination and carboborylation (with oxidative workup) provided products in 56% yield (1/>100 cis/trans) and 69% yield (1/11 cis/trans), respectively.
Article
Chemistry, Organic
Xiao-Xiao Li, Jian-Sen Wang, Xiao-Xia You, Rong-Lin Zhong, Zhong-Min Su
Summary: The Pd-catalyzed borylation of fluorobenzene was investigated theoretically, and it was found that the reaction proceeds through an unprecedented 3 + 6-membered ring transition state. This transition state involves the interaction of one LiHMDS as a ligand and another LiHMDS providing essential Li·N and Li·F interactions, effectively overcoming the destabilization caused by the distortion of the phenyl-F bond.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
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, Applied
Yaoguang Sheng, Yi Gao, Bingbing Duan, Mengxia Lv, Yao Chen, Mengjie Yang, Jianmin Zhou, Guang Liang, Zengqiang Song
Summary: A versatile and efficient method for the coupling of maleimides and indoles at the C7-position has been established under Rh(III) catalysis. The protocol is compatible with various functional groups, and yields diverse 3-(indol-7-yl) maleimides and 3-(indol-7-yl)succinimides by switching reaction conditions. Deuteration studies and control experiments have been carried out to explore the mechanism of this transformation.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Yixiu Ge, Zaozao Qiu, Zuowei Xie
Summary: A palladium-catalyzed selective tetrafunctionalization method for o-carborane derivatives has been developed, providing 3,6-dialkenyl-4,11-R-2-o-carboranes and 4,7-dialkenyl-5,11-R-2-o-carboranes in moderate to excellent yields. This study represents a new strategy for the selective synthesis of polyfunctionalized o-carborane derivatives in a one-pot process.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Tamilarasu Murugesan, Chinraj Sivarajan, Chithra Mohan Jayakumari, Rajat Kumar Singh, Sivaranjana Reddy Vennapusa, Alagiri Kaliyamoorthy
Summary: In this study, a straightforward access to C2-biarylated indole derivatives was achieved through palladium-catalyzed C-H activation strategy, with yields ranging from 24% to 92%. The UV/visible absorption and fluorescence properties of the resulting products were explored, showing that these compounds may exhibit atropisomerism at room temperature based on calculated dihedral angle and rotational barrier values.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Bartlomiej Sadowski, Binbin Yuan, Zhipeng Lin, Lutz Ackermann
Summary: In this study, electrocatalytic peri C-H alkenylation of 1-naphthols was achieved using rhodium(III) catalysis under constant current electrolysis conditions. This strategy offers a wide scope, good functional group tolerance, and high site- and stereoselectivity.
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, Multidisciplinary
Barry M. Trost, Zhijun Zuo
Summary: A novel Pd-0-catalyzed highly selective [3+2] spiroannulation reaction has been developed for rapid assembly of a new class of [5,5] spirocyclic carbo- and heterocycles. The regioselectivity of the reaction can be controlled by fine-tuning the Pd-pi-allyl intermediate, with excellent toleration of various coupling partners and enantioselectivities demonstrated through further transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Xin Fu, Yu Hao, He-Yuan Bai, Abing Duan, Shu-Yu Zhang
Summary: The cobalt-catalyzed regio- and enantioselective gamma-amination of beta,gamma-unsaturated N-acylpyrazoles has been achieved, delivering the corresponding products with good regio- and enantioselectivity. DFT calculations were used to explain the selectivity of this gamma-amination, and the chiral products were easily converted into chiral gamma-amino acid derivatives.
Article
Chemistry, Organic
Xuefei Li, Xing Gao, Chun-Yang He, Xingang Zhang
Summary: A nickel-catalyzed reductive cross-coupling reaction has been reported for the coupling of industrial chemical CF3CH2Cl with (hetero)aryl bromides and chlorides. The reaction is synthetically simple, exhibits high functional group tolerance, and has been demonstrated to be useful for late-stage modification of pharmaceuticals, providing a convenient route for medicinal chemistry.
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, 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)
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.
