Article
Multidisciplinary Sciences
Shuaishuai Wang, Tingrui Li, Chengyihan Gu, Jie Han, Chuan-Gang Zhao, Chengjian Zhu, Hairen Tan, Jin Xie
Summary: This article reports on an iron-catalyzed reaction for efficient construction of aromatic tertiary amines, which is important in drug discovery and organic chemistry. The reaction employs a radical tandem C-N coupling strategy and can synthesize nonsymmetric aromatic tertiary amines under mild conditions.
NATURE COMMUNICATIONS
(2022)
Article
Multidisciplinary Sciences
Zhe Dong, David W. C. MacMillan
Summary: Metal-catalysed cross-couplings are widely used for the formation of C-C bonds, but alkyl cross-couplings using alcohols as coupling partners remain relatively underdeveloped. A new method for direct deoxygenative cross-coupling of free alcohols has been developed, showing potential for a wide range of applications, including the pharmaceutical industry. This technology represents a general strategy for combining in situ alcohol activation with transition metal catalysis.
Article
Chemistry, Multidisciplinary
Sisi Wu, Weijia Shi, Gang Zou
Summary: Liquid-assisted grinding has been successfully used to eliminate the need for chemical activators and anhydrous solvents in nickel-catalyzed, manganese-mediated cross-electrophile coupling between aryl and alkyl bromides. The optimal condition obtained through a combined evaluation of reaction and mechanical parameters allowed for the synthesis of various n-alkyl aromatics with different functional groups in good yields with a 1 mol% catalyst loading. The practical application of liquid-assisted grinding-enabled aryl/alkyl cross-electrophile coupling has been demonstrated in the gram-scale synthesis of 6-methoxytetralone.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Organic
Tian Cao, Yi-Peng Luo, Long Cheng, Jia-Li Zhao, Qiao-Sen Jia, Shu Zhang, Xiang-Wei Liu
Summary: This article describes a novel method for the de novo catalytic synthesis of diarylamines through a palladium-catalyzed reductive Buchwald-Hartwig amination of nitroarenes with aryl (pseudo)halides. The use of upstream nitroarenes as arylamine surrogates, the choice of bis(pinacolato)diboron (B(2)pin(2)) as a stoichiometric reducing agent, and the wide scope of substrates including (hetero)aryl halides (Cl, Br, and I) and aryl triflates are the notable features of this protocol. Furthermore, its successful application in the synthesis of advanced intermediates and active pharmaceutical ingredients provides an alternative and cost-effective approach to the synthesis of diarylamine-incorporated molecules. Preliminary mechanistic investigations suggest the involvement of amine and nitrosoarene intermediates in this reductive process.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Fei Li, Weikang Xiong, Geyang Song, Yonggang Yan, Gang Li, Chao Wang, Jianliang Xiao, Dong Xue
Summary: A general and efficient photochemical C-N coupling method for (hetero)aryl chlorides with hydrazides is presented. The reaction is catalyzed by a Ni(II)-bipyridine complex and does not require an external photosensitizer, making it highly practical. This method demonstrates a wide substrate scope (54 examples) and excellent functional group tolerance, and has been successfully applied to the synthesis of rizatriptan.
Article
Chemistry, Multidisciplinary
Yunhui Feng, Hang Luo, Fangnian Yu, Qian Liao, Luqing Lin
Summary: Here, we present a visible-light-promoted single nickel catalysis for achieving various C-N couplings of aryl chlorides/bromides and diverse N-nucleophiles using sodium iodide as the activator. The single nickel catalyst plays a dual role in halogen exchange and C-N coupling, which are crucial for obtaining the desired coupling products. This catalytic process eliminates the need for an exogenous photocatalyst and offers a sustainable and efficient approach for mild C-N coupling. Experimental studies, along with UV-vis and NMR analyses, demonstrate that the halogen exchange between both Ni-II and Ni-III-halide complexes and the iodide anion is a significant process in the formation of coupling products.
Article
Chemistry, Organic
Jinpeng Li, Changyu Huang, Daheng Wen, Qingshu Zheng, Bo Tu, Tao Tu
Summary: A nickel-catalyzed amination of aryl chlorides with diverse amides via C-N bond cleavage has been successfully achieved under mild conditions. The protocol offers a broad substrate scope with excellent functional group tolerance at a low catalyst loading, making it powerful for synthesizing various aromatic amines. Selective coupling of aryl chlorides to the amino fragments of amides rather than the carbonyl moieties expands the usage of inactive amides.
Article
Chemistry, Physical
Zuxiao Zhang, Duong T. Ngo, David A. Nagib
Summary: A dual catalytic strategy involving an Ir photocatalyst and a Cu complex enables regioselective amination and cross-coupling of allyl alcohols with various nucleophiles. This approach allows for the formation of N-radicals via an energy transfer mechanism followed by interception of alkyl radicals for radical amino-functionalizations of olefins. Insights into the nature of Cu-based radical interception are provided through stereo, regio, and kinetic probes.
Article
Chemistry, Physical
Geyang Song, Ding-Zhan Nong, Qi Li, Yonggang Yan, Gang Li, Juan Fan, Wei Zhang, Rui Cao, Chao Wang, Jianliang Xiao, Dong Xue
Summary: This study demonstrates an easy, efficient, and economic method for synthesizing anilines. By directly exciting light, the amination of aryl halides with ammonium salts can be catalyzed using a Ni(OAc)2-bipyridine complex, allowing a broad range of aryl chlorides and bromides to be converted into primary (hetero)arylamines without the need for an external photosensitizer. The photoinduced generation of Ni(I)-bipyridine species is believed to play a key role in this catalytic cycle.
Article
Chemistry, Multidisciplinary
Xiaolei Huang, Shenghan Teng, Yonggui Robin Chi, Wenqiang Xu, Maoping Pu, Yun-Dong Wu, Jianrong Steve Zhou
Summary: The nickel-catalyzed intermolecular Heck reaction of cycloalkenes with aryl triflates, mesylates, and tosylates shows excellent enantiomeric ratios. Additionally, the asymmetric reductive Heck reaction is also applicable to a 2-cyclopentenone ketal, equivalent to conjugate arylation of the enone itself.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Shuai Zhong, Guo-Jun Deng, Zhiqi Dai, Huawen Huang
Summary: This study presents a visible-light-induced photoredox system for efficient reductive deoxygenation of N-heteroaryl ketones and alcohols. The combinational use of 4CzIPN as photocatalyst and LiBr as additive in acidic media constitutes a tireless electron shuttle mechanism, facilitating the electron transfer process. The reduction course involves proton-coupled electron transfer, spin-center shift, and single-electron-transfer processes, leading to a mild route for the synthesis of pharmaceutically valuable alkyl and benzyl N-containing heteroarenes.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
L. Xue, D. Xue
Summary: This article briefly discusses recent advances in catalytic hydroxylation reactions for the synthesis of phenols, with a focus on the efficient use of water as a hydroxide reagent. This methodology allows for the synthesis of diverse phenols and enables the hydroxylation of multifunctional pharmaceutically relevant aryl halides.
Article
Chemistry, Organic
Hua-Dong He, Zhi-Kai Zhang, Hao-Bo Tang, Yuan-Qing Xu, Xiao-Bo Xu, Zhong-Yan Cao, Hao Xu, Yang Li
Summary: A practical method for the synthesis of N,N-dialkyl anilines via reductive dialkylation has been developed using inexpensive substrates and cheap NiI2 as the key promoter. This method demonstrates high functional group tolerance and can be used for the synthesis and modification of drugs or pesticides.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Raghu N. Dhital, Abhijit Sen, Hao Hu, Rikako Ishii, Takuma Sato, Yoko Yashiroda, Hiromi Kimura, Charles Boone, Minoru Yoshida, Yushi Futamura, Hiroyuki Hirano, Hiroyuki Osada, Daisuke Hashizume, Yasuhiro Uozumi, Yoichi M. A. Yamada
Summary: In this study, a phenylboronic ester-activated aryl iodide-selective Buchwald-Hartwig-type amination was developed. The reaction proceeds smoothly to afford the corresponding amines in high yields in the presence of phenylboronic ester. A wide variety of aryl iodides can be applied, while aryl chlorides and bromides remain intact. The reaction is catalyzed by the phenylboronic ester and shows potential antifungal activity.
Article
Biochemistry & Molecular Biology
Nil Sanosa, Pedro Ruiz-Campos, Diego Ambrosi, Diego Sampedro, Ignacio Funes-Ardoiz
Summary: Photoredox catalysis offers an alternative method for cross-coupling reactions and enables new reactivities. A recent study demonstrated that abundant alcohols and aryl bromides can efficiently promote coupling through the Ir/Ni dual photoredox catalytic cycle, although its mechanism remains unexplored. In this study, we utilized DFT calculations to comprehensively investigate the catalytic cycle and found that nickel catalysts can effectively promote this reactivity. Two different mechanistic scenarios were explored, suggesting that dual catalytic cycles operate simultaneously depending on the concentration of the alkyl radical.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Organic
Kun Wang, Saisai Niu, Xin Guo, Weijun Tang, Dong Xue, Jianliang Xiao, Huaming Sun, Chao Wang
Summary: This research discovers a new method to convert prochiral racemic allylic alcohols to enantioenriched chiral alcohols bearing adjacent stereocenters using a diamine diphosphine Ru complex and tBuOK catalyst. The protocol exhibits a wide substrate scope and high selectivities, and can be applied to the synthesis of enantioenriched chromane and indane compounds.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Xiaohui Zhang, Wei Ma, Jinyu Zhang, Weijun Tang, Dong Xue, Jianliang Xiao, Huaming Sun, Chao Wang
Summary: The asymmetric hydroalkylation of racemic allylic alcohols has been developed for the synthesis of chiral amino acid derivatives with two remote chiral centers by borrowing hydrogen catalysis. The stereoselectivities are controlled by a single chiral Ru catalyst via a dynamic kinetic asymmetric transformation process and an interesting diastereoselectivity amplification process of the product.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Yonggang Yan, Jinjin Sun, Gang Li, Liu Yang, Wei Zhang, Rui Cao, Chao Wang, Jianliang Xiao, Dong Xue
Summary: A light-promoted Ni-catalyzed cyanation reaction using 1,4-dicyanobenzene as a cyanating agent is described. Various aryl bromides, chlorides, and druglike molecules are converted to their corresponding nitriles (65 examples). Mechanistic studies reveal that under irradiation, the Ni(II)(dtbbpy)(p-C6H4CN)(CN) oxidative addition product undergoes homolytic cleavage of the Ni-aryl bond to generate an aryl radical and a Ni(I)-CN species, which initiates subsequent cyanation reactions.
Article
Chemistry, Multidisciplinary
Xiaoyun Wu, Wei Ma, Weijun Tang, Dong Xue, Jianliang Xiao, Chao Wang
Summary: A Fe-catalyzed amidation of allylic alcohols with chiral tert-butylsulfinamide has been developed for the synthesis of chiral sulfinamide olefin derivatives. The reaction proceeds under mild conditions with water as the only by-product.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Geyang Song, Ding-Zhan Nong, Jing-Sheng Li, Gang Li, Wei Zhang, Rui Cao, Chao Wang, Jianliang Xiao, Dong Xue
Summary: The Buchwald-Hartwig C-N coupling reaction is widely used in medicinal chemistry. Ni-based catalysts have attracted great attention due to their lower cost and higher reactivity towards less reactive aryl chlorides. However, there is currently no universal Ni catalytic system available for the coupling of electron-rich and electron-poor aryl halides with primary and secondary alkyl amines. In this study, a Ni(II)-bipyridine complex is reported to catalyze efficient C-N coupling of aryl chlorides and bromides with various primary and secondary alkyl amines under direct excitation with light. The feasibility and applicability of this protocol in organic synthesis are demonstrated with over 200 examples.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Yuxuan Liu, Qi Luo, Qian Qiang, Hua Wang, Yangming Ding, Chao Wang, Jianliang Xiao, Changzhi Li, Tao Zhang
Summary: The sustainable synthesis of quinoxaline derivatives from lignin beta-O-4 model compounds under transition-metal-free conditions has been achieved for the first time in this study. Mechanistic studies showed that this transformation involves highly coupled cascade steps. With this method, a wide range of functionalized quinoxalines, including an important drug compound, were successfully synthesized, demonstrating the potential application of lignin in pharmaceutical synthesis.
Article
Chemistry, Organic
Liu Yang, Yonggang Yan, Ni Cao, Jing Hao, Gang Li, Wei Zhang, Rui Cao, Chao Wang, Jianliang Xiao, Dong Xue
Summary: A highly efficient hydroxylation of (hetero)aryl halides using water as a hydroxyl source via Ni catalysis promoted by PhSiH3 under thermal catalysis is described. This methodology provides a general procedure for the synthesis of diverse multifunctional pharmaceutically phenols and polyphenols, some of which are challenging to be synthesized using literature methods. Mechanism studies reveal that the addition of PhSiH3 leads to the generation of active Ni(I) species, which catalyze the hydroxylation through a Ni(I)-Ni(III) pathway.
Article
Chemistry, Physical
Geyang Song, Ding-Zhan Nong, Qi Li, Yonggang Yan, Gang Li, Juan Fan, Wei Zhang, Rui Cao, Chao Wang, Jianliang Xiao, Dong Xue
Summary: This study demonstrates an easy, efficient, and economic method for synthesizing anilines. By directly exciting light, the amination of aryl halides with ammonium salts can be catalyzed using a Ni(OAc)2-bipyridine complex, allowing a broad range of aryl chlorides and bromides to be converted into primary (hetero)arylamines without the need for an external photosensitizer. The photoinduced generation of Ni(I)-bipyridine species is believed to play a key role in this catalytic cycle.
Article
Chemistry, Multidisciplinary
Wang Miao, Jinyu Zhang, Yanyan Yang, Weijun Tang, Dong Xue, Jianliang Xiao, Huaming Sun, Chao Wang
Summary: The transformation of alcohols into value-added products is of great importance, and this study achieved the selective functionalization of a sp(3) C-H bond on the alkyl side chain of an alcohol, expanding the chemical space of alcohols using the borrowing hydrogen strategy.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yuan Gao, Zhijun Wang, Xinyu Zhang, Min Zhao, Shuai Zhang, Chao Wang, Liang Xu, Pengfei Li
Summary: In this study, novel chiral half-sandwich iridium catalysts were designed and synthesized, which enabled the preparation of a broad range of α-chiral (hetero)aryl amines with high yield and enantioselectivity. The optimized catalyst and azeotropic mixture of formic acid and triethylamine were used as the hydrogen source under mild and operationally simple conditions. This work introduced an effective chiral catalyst for the simplified synthesis of medicinally important chiral amines, and also provided a rare example of robust enantioselective transition-metal catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Geyang Song, Qi Li, Ding-Zhan Nong, Jiameng Song, Gang Li, Chao Wang, Jianliang Xiao, Dong Xue
Summary: This paper describes a photochemical C-N coupling reaction of less reactive aryl chlorides with primary and secondary amides using a Ni catalyst without an external photocatalyst. The reaction proceeds under light irradiation (390-395 nm) with a soluble organic amine as the base, resulting in the successful synthesis of a wide range of N-aryl amides from (hetero)aryl chlorides. Mechanistic studies suggest that the amidation occurs via a Ni(I)-Ni(III) catalytic cycle.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Fei Li, Weikang Xiong, Geyang Song, Yonggang Yan, Gang Li, Chao Wang, Jianliang Xiao, Dong Xue
Summary: A general and efficient photochemical C-N coupling method for (hetero)aryl chlorides with hydrazides is presented. The reaction is catalyzed by a Ni(II)-bipyridine complex and does not require an external photosensitizer, making it highly practical. This method demonstrates a wide substrate scope (54 examples) and excellent functional group tolerance, and has been successfully applied to the synthesis of rizatriptan.
Article
Chemistry, Multidisciplinary
Yonggang Yan, Gang Li, Jiani Ma, Chao Wang, Jianliang Xiao, Dong Xue
Summary: This paper reports the photoinduced generation of highly reactive ketyl radicals and their application in C-C coupling, without the need for any external photocatalyst.
