Article
Chemistry, Applied
Masami Kuriyama, Genki Maeda, Kazuya Kamata, Yusuke Kodama, Kosuke Yamamoto, Osamu Onomura
Summary: The nickel-catalyzed cross-coupling of bromodifluoromethylphosphonates with arylboron reagents was achieved using a 1,10-phenanthroline-type ligand. Functionalized and heterocycle-containing boroxines were suitable partners for this reaction, and the catalytic modification of biologically active molecules, such as fenofibrate and indomethacin, was successfully accomplished. Moreover, the gram-scale reaction proceeded smoothly with a high yield of desired product.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Review
Chemistry, Multidisciplinary
Emily K. Reeves, Emily D. Entz, Sharon R. Neufeldt
Summary: Chemodivergent cross-couplings refer to reactions in which one potentially reactive functional group can be made to react based on choice of conditions. Factors influencing selectivity include catalyst ligation state, solvent polarity, and metal identity.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Zhenghong Zhou, Jimin Yang, Bo Yang, Yang Han, Lijuan Zhu, Xiao-Song Xue, Feng Zhu
Summary: This study presents a pioneering example of nickel-catalysed enantioconvergent Stille cross-coupling reactions. The reactions result in the formation of C-C bonds in good to high yields with excellent stereoselectivity, providing a practical and cost-effective method for synthesis. The innovative use of synergistic photoredox/nickel catalysis enables a novel single-electron transmetalation process, opening up new research possibilities in the field of Stille reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Takeshi Fujita, Yutaro Kobayashi, Ikko Takahashi, Ryutaro Morioka, Tomohiro Ichitsuka, Junji Ichikawa
Summary: Nickel-catalyzed reductive cross-coupling of allylic difluorides with aryl iodides was successfully achieved, leading to the synthesis of a series of gamma-arylated monofluoroalkenes with moderate to high yields and high Z-selectivities. Mechanistic studies indicated that the cleavage of C-I bonds in aryl iodides and C-F bonds in allylic difluorides occurred through oxidative addition and beta-fluorine elimination, respectively.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Felipe Verdugo, Ricardo Rodino, Martin Calvelo, Jose Luis Mascarenas, Fernando Lopez
Summary: The reactivity of carbonyl-tethered alkylidenecyclopropanes (ACPs) can be directed towards tandem cycloisomerization/cross-coupling processes by using Pd-0 catalysts with phosphorus-based monodentate ligands. This allows for the synthesis of a wide variety of highly functionalized cyclic alcohols and amines through the formation of key pi-allyl oxapalladacyclic intermediates which are trapped with external nucleophilic partners.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Jian Luo, Bo Hu, Wenda Wu, Maowei Hu, T. Leo Liu
Summary: This study reports a redox neutral electrochemical C(sp(2))-C(sp(3)) cross-coupling reaction conducted under ambient conditions using nonprecious metal catalysts. The reaction demonstrated good yields and a broad scope, with potential applications in pharmaceuticals and natural amino acid modification. The method, which proceeds through an unconventional radical transmetalation mechanism, is highly productive and expected to have widespread applications in organic synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Bo-Shuai Mu, Yang Gao, Fu-Ming Yang, Wen-Biao Wu, Ying Zhang, Xin Wang, Jin-Sheng Yu, Jian Zhou
Summary: We have developed bifunctional trifluoromethylsilyl reagents for selective trifluoromethylation. The newly developed reagent allows highly enantioselective trifluoromethylations of ketones and enables the synthesis of chiral trifluoromethylated oxasilacyclopentanes. Theoretical studies have revealed the importance of nonclassical C-H...F-C interactions in stabilizing the transition state and the enhancement of such interactions by the presence of a chlorine atom for better enantiofacial control.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Biping Xu, Weiping Su
Summary: In this paper, we report a transition metal-free, operationally simple, general method for the straightforward synthesis of 2-substituted benzoxazoles from readily available cyclohexanones and aliphatic primary amines. The key to the success of this method is the use of TEMPO as a mild oxidant, which selectively oxidizes the reaction intermediates through its multiple reactivity modes, allowing the individual steps to proceed in succession. This protocol demonstrates high reliability and excellent functional-group tolerance, enabling the synthesis of structurally diverse products, including marketed drugs, drug candidates, and natural products that are unattainable by existing methods.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Bijan Mirabi, Austin D. Marchese, Mark Lautens
Summary: In this study, a nickel-catalyzed cross-electrophile coupling reaction of aryl chlorides and heteroaryl chlorides was reported, enabled by a synergistic combination of halide effects and the addition of a magnesium salt. Electronic-deficient aryl chlorides were found to perform the best in the reaction, and preliminary mechanistic evidence showed that MgCl2 is crucial for accelerating the reduction of Ni(II) while small quantities of iodide lead to improved yields.
Article
Chemistry, Organic
Juanjuan Wu, Hongli Wu, Xinyu Liu, Yuekun Zhang, Genping Huang, Chun Zhang
Summary: A nickel-catalyzed reductive cross-coupling reaction has been developed for the synthesis of chiral α-CF3 ketones with high enantioselectivity and good functional group tolerance. The study of late-stage transformation demonstrated its applicability in preparing bioactive compounds. Control experiments further indicated the importance of the α-trifluoromethyl group in this reaction.
Article
Chemistry, Multidisciplinary
Chengsen Cui, Mingji Dai
Summary: We present a highly efficient and convergent strategy for synthesizing UCS1025A and its diastereomer tetra-epi-UCS1025A. UCS1025A is a representative member of the naturally occurring pyrrolizidinone polyketides, some of which exhibit potent antibacterial, antifungal, and anticancer activities. Our approach involves a tandem carbonylative Stille cross coupling and Diels-Alder reaction to form a key C-C bond and construct the trans-decalin system. The process uses carbon monoxide as a linchpin to connect a vinyl triflate and a vinylstannane, resulting in the desired enone moiety for subsequent intramolecular Diels-Alder cyclization. Additionally, our synthesis provides a versatile method for synthesizing other pyrrolizidinone-containing polyketides.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Applied
Amreen K. Bains, Ayanangshu Biswas, Debashis Adhikari
Summary: The study describes an isolable, air-stable homogeneous nickel catalyst for dehydrogenative cross-coupling reaction between secondary and primary alcohols to selectively produce alpha-alkylated ketone products in a one-pot reaction. Preliminary mechanistic investigation suggests a radical mechanism following borrowing hydrogen reaction.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Zhengzhen Diao, Yu Feng, Jida Zhang, Xin Wang, Hansheng Li, Chen Ding, Zhen Zhou, Xinjin Li
Summary: A mild and efficient method for the synthesis of 2,2-difluoroethylated (hetero)aryl halides using readily available 2-chloro-1,1-difluoroethane has been developed. The reductive cross-coupling reaction is synthetically simple and exhibits good functional group tolerance. This approach provides a facile access to synthesize 2,2-difluoroethylated molecules for drug discovery.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Applied
Lilian Geniller, Marc Taillefer, Florian Jaroschik, Alexis Prieto
Summary: The Ni-photoredox catalyzed desulfurative cross-coupling reaction enables the synthesis of various unsymmetrical diarylmethane molecules under mild reaction conditions, providing new transformations of abundant, naturally occurring thiols.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Yangzhong Qin, Rui Sun, Nikolas P. Gianoulis, Daniel G. Nocera
Summary: The researchers conducted a comprehensive mechanistic study of photoredox nickel-catalyzed C-S cross-coupling, revealing a self-sustained productive Ni(I/III) cycle, the role of in situ formed pyridinium iodide as a dominant quencher, and critical intermediates in the reaction pathway. These mechanistic insights not only provided a complete reaction cycle but also allowed for optimization of reaction efficiency and broadening the substrate scope.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
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
Lun An, Patricia De La Torre, Peter T. Smith, Mina R. Narouz, Christopher J. Chang
Summary: We present a supramolecular approach to catalyzing photochemical CO2 reduction using second-sphere porosity and charge effects. This work establishes that synergistic pendants in the secondary coordination sphere can be leveraged as a design element to augment catalysis at primary active sites within confined spaces.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
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)
Review
Chemistry, Multidisciplinary
Patricia de la Torre, Lun An, Christopher J. Chang
Summary: The catalytic reduction of carbon dioxide (CO2) using sustainable energy inputs is a promising strategy for transforming atmospheric carbon into valuable chemical products. This review highlights the development of catalysts for selective and efficient CO2 conversion through electrochemical and photochemical methods. Porous platforms, such as covalent organic frameworks, metal-organic frameworks, and porous molecular cages, integrated with well-defined molecular elements, offer increased active site exposure, stability, and water compatibility for enhanced CO2 reduction activity.
ADVANCED MATERIALS
(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
Lun An, Mina R. Narouz, Peter T. Smith, Patricia De La Torre, Christopher J. Chang
Summary: A supramolecular strategy integrating two-dimensional cobalt porphyrin units into a three-dimensional porous organic cage architecture was proposed for enhancing the electrochemical nitrate reduction reaction (NO3RR). The resulting structure exhibited improved catalyst stability and activity, leading to a higher turnover frequency of 56 s(-1) for ammonia production. These findings highlight the effectiveness of incorporating 2D molecular units into 3D confined microenvironments for enhancing electrocatalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
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.
