Article
Chemistry, Physical
Shaofang Zhou, Tiantian Liu, Xiaoguang Bao
Summary: This study describes a new strategy for the direct C(sp3)-H amidation using photoredox-mediated hydrogen atom transfer and transition-metal catalysis under mild conditions. The method provides good reactivity and site selectivity for the construction of C(sp3)-N bonds and can be applied to the late-stage modification of complex molecules.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Physical
Shaofang Zhou, Kang Lv, Rui Fu, Changlei Zhu, Xiaoguang Bao
Summary: The study demonstrates the successful construction of aliphatic C-N bonds via nickel/photoredox dual catalysis, utilizing single electron transfer and photocatalyst-induced mechanisms. Synergistic experimental and computational studies propose a reaction pathway involving oxidative quenching of the photocatalyst and a potential Ni-catalyzed cycle for C(sp(3))-N bond formation.
Article
Chemistry, Physical
Pei-Pei Xie, Zhi-Xin Qin, Shuo-Qing Zhang, Xin Hong
Summary: This study elucidates the controlling factors of Ni/PCy3-catalyzed amide C-N bond activation barrier using density functional theory calculations and distortion/interaction analysis. It is found that substrate distortion is the key factor that differentiates amide reactivity, leading to two distinctive structure-activity relationships for planar and twisted amides. Moreover, the understanding of the structure-activity relationship provides a rational and predictive basis for future reaction designs involving transition metal-catalyzed amide C-N bond activation.
Review
Chemistry, Applied
Paola Acosta-Guzman, Andrea Ojeda-Porras, Diego Gamba-Sanchez
Summary: The construction of amide bonds is of great interest due to their prevalence in bioactive molecules. This review presents the most viable strategies for constructing amide bonds, with a focus on recent developments in the field.
ADVANCED SYNTHESIS & CATALYSIS
(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, Multidisciplinary
Qingyao Li, Peng Dai, Haidi Tang, Muliang Zhang, Jie Wu
Summary: The significance of amide functional groups in organic synthesis and pharmaceutical studies is widely recognized. However, current synthesis methods often involve the use of stoichiometric activating reagents and metallic reductants, leading to the production of toxic chemical waste. In this study, a photo-mediated hydrogen atom transfer catalysis is developed for direct reductive amidation reaction, which avoids the use of metallic reductants and toxic chemical waste. The method provides an efficient and practical strategy for the synthesis of amides.
Article
Chemistry, Organic
Ni Xiong, Yuanqi Dong, Bin Xu, Yang Li, Rong Zeng
Summary: This study describes a mild protocol for amide formation using nitroarenes as nitrogen sources and an inexpensive iron complex as a catalyst. The method utilizes pH-neutral conditions and avoids the use of strong oxidants or reductants, allowing for tolerance of a wide range of aldehydes and nitroarenes with various functional groups.
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, Multidisciplinary
Jinhong Chen, Hao Wang, Craig S. Day, Ruben Martin
Summary: A nickel-catalyzed site-selective intermolecular amidation of saturated C(sp(3))-H bonds has been reported, allowing for the introduction of amide functionalities at specific sites. This method exhibits a predictable reactivity pattern, offering a complementary reactivity profile to existing oxidative processes or metal-catalyzed C(sp(3))-N bond-forming reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Qing Wang, Shengyang Ni, Lei Yu, Yi Pan, Yi Wang
Summary: This study presents a convenient method for the conversion of light alkanes to high value-added products by utilizing high-valent tungsten and nickel catalysis. The use of photoexcited metal relay enables the activation of inert C-H bonds and stabilization of intermediates, leading to the rapid construction of C(sp(3))-N bonds.
Article
Chemistry, Organic
Jessica M. L. Elwood, Martyr C. Henry, J. Daniel Lopez-Fernandez, Jenna M. Mowat, Mhairi Boyle, Benjamin Buist, Keith Livingstone, Craig Jamieson
Summary: We have reported the use of N-2,4-dinitrophenyltetrazoles as latent active esters (LAEs) in the synthesis of amide bonds. This method allows the generation of an HOBt-type active ester without the need for exogenous coupling agents. The methodology is applicable to a wide range of substrates, providing quantitative yields. The versatility and functional group tolerance were demonstrated in the one-step synthesis of various pharmaceutical agents and the N-acylation of resin-bound peptides.
Article
Chemistry, Physical
Qing Wang, Shengyang Ni, Lei Yu, Yi Pan, Yi Wang
Summary: This study presents a rapid method for constructing C(sp(3))-N bonds from light alkanes using high-valent tungsten and nickel catalysts with amine/amide electrophile reagents. The photoexcited metal relay serves as a powerful tool for activating inert sp(3)-hybridized C-H bonds and stabilizing C-Ni(III)-N intermediates.
Article
Chemistry, Multidisciplinary
Judith Sala, Lorena Capdevila, Cristina Berga, Araceli de Aquino, Laura Rodriguez, Silvia Simon, Xavi Ribas
Summary: In this study, a stepwise synthesis of new nanographenes and polycyclic aromatic hydrocarbons (PAHs) via Scholl ring fusion is reported. The aromatic homologation compounds, obtained through one-step Ni-catalysed Csp2-F functionalization, are shown to be valid precursors for the Scholl reaction. Furanol-bearing PAHs are described for the first time by screening experimental conditions. DFT calculations provide mechanistic insights into the formation of furanol PAHs under moderately acidic conditions. All synthesized PAHs and nanographenes exhibit moderate/weak fluorescent properties, and the crystallized PAHs show some degree of curvature and are obtained as racemic mixtures. Enantiomeric separation of one furanol-bearing PAH allows for the study of its chiroptical CD properties.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Feng-Ping Zhang, Rong-Hua Wang, Jiang-Fei Li, Hao Chen, Madala Hari Babu, Mengchun Ye
Summary: In this study, an intermolecular carbophosphination reaction of alkynes with 5-membered phosphole oxides was successfully realized using a Ni-Al bimetallic catalyst, leading to the formation of a series of 7-membered phosphepines in high yields up to 94%.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Mo Chen, John Montgomery
Summary: Regio- and enantioselective functionalization of heteroarene C-H bonds in the absence of directing groups has been a long-standing challenge. In this study, we developed a new approach for intermolecular enantioselective C-H alkylation of heteroarenes using nickel catalysts. The reaction can be carried out under mild conditions without the need for Lewis acid co-catalysts. Synthesis of NHC nickel complexes stabilized with 1,5-hexadiene improved the functional group tolerance and heteroarene scope. Mechanistic investigations revealed a ligand-to-ligand hydrogen transfer pathway.
Article
Chemistry, Multidisciplinary
Cheng-Jian Zhang, Tian-Cheng Zhu, Xiao-Han Cao, Xin Hong, Xing-Hong Zhang
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2019)
Article
Chemistry, Multidisciplinary
Pan-Pan Chen, Erika L. Lucas, Margaret A. Greene, Shuo-Qing Zhang, Emily J. Tollefson, Lucas W. Erickson, Buck L. H. Taylor, Elizabeth R. Jarvo, Xin Hong
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2019)
Article
Chemistry, Multidisciplinary
Hua-Chen Lin, Pei-Pei Xie, Zhen-Yao Dai, Shuo-Qing Zhang, Pu-Sheng Wang, Yu-Gen Chen, Tian-Ci Wang, Xin Hong, Liu-Zhu Gong
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2019)
Article
Chemistry, Organic
Zheng-Bing Zhang, Chong-Lei Ji, Ce Yang, Jie Chen, Xin Hong, Ji-Bao Xia
Article
Chemistry, Organic
Ji-Ren Liu, Ye-Qing Duan, Shuo-Qing Zhang, Lu-Jing Zhu, Yuan-Ye Jiang, Siwei Bi, Xin Hong
Article
Chemistry, Applied
Feng Li, Xu Bai, Yuan Cai, Han Li, Shuo-Qing Zhang, Feng-Hua Liu, Xin Hong, Youjun Xu, Shi-Liang Shi
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2019)
Article
Chemistry, Multidisciplinary
Yin Xu, Qing Sun, Tong-De Tan, Ming-Yang Yang, Peng Yuan, Shao-Qi Wu, Xin Lu, Xin Hong, Long-Wu Ye
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2019)
Article
Chemistry, Analytical
Qian Sun, Jiajia Xu, Chonglei Ji, Mazen S. S. Shaibani, Zheng Li, Kahleong Lim, Chengwu Zhang, Lin Li, Zhipeng Liu
ANALYTICAL CHEMISTRY
(2020)
Article
Chemistry, Organic
Tongliang Zhou, Pei-Pei Xie, Chong-Lei Ji, Xin Hong, Michal Szostak
Article
Chemistry, Physical
Hechen Wu, Xiao-Nan Wu, Xuegang Liu, Chonglei Ji, Wei Li, Ling Jiang, Hua Xie, Mingfei Zhou
Summary: The reaction of the iridium dimer anion [Ir-2](-) with acetylene in the gas phase can completely cleave the robust C C triple bond of acetylene, forming product anions with varying numbers of carbon and hydrogen atoms.
JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
Article
Chemistry, Organic
Yijun Shi, Chong-Lei Ji, Chengwei Liu
Summary: This study presents a general and practical method for the addition of aryl halides and alkynes to norbornenes using palladium catalysis. Norbornenes function as unsaturated acceptors for aryl and alkynyl groups, leading to the formation of saturated bridged C-C bonds. The optimized Pd(OAc)(2)/PCy3HBF4 system enables the difunctionalization of norbornenes by cleavage of C-X/C-H bonds and highly selective formation of C(sp(3))-C(sp(2))/C(sp(3))-C(sp) bonds. Broad substrate scope and excellent functional group tolerance highlight the high efficiency of this approach. Mechanistic insights were gained through experimental and DFT-based studies.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Hechen Wu, Xiao-Nan Wu, Xiaoyang Jin, Yangyu Zhou, Wei Li, Chonglei Ji, Mingfei Zhou
Summary: The structure of the [Rh2C3](+) ion and its reaction with CH4 in the gas phase have been studied, revealing the formation of different products. When using isotopic-labeled (CH4)-C-13 sample, a specific [(Rh2C)-C-13](+) ion is also formed. The reactions are thermodynamically exothermic and involve the activation of C-H bonds and hydrogen atom transfer at the two Rh centers.
Article
Chemistry, Multidisciplinary
Tongliang Zhou, Chong-Lei Ji, Xin Hong, Michal Szostak
Article
Multidisciplinary Sciences
Chengwei Liu, Chong-Lei Ji, Zhi-Xin Qin, Xin Hong, Michal Szostak
Article
Chemistry, Organic
Xin Li, Shuo-Qing Zhang, Xin Hong
ORGANIC & BIOMOLECULAR CHEMISTRY
(2019)