Article
Chemistry, Organic
Qin Shi, Haiyan Hu, Minxing Du, Yajun Sun, Yudong Li, Yuehui Li
Summary: In this study, CO2/H2 was used as a methylation reagent for selective C-H methylation of heteroarenes. The reaction was catalyzed by cobalt/B(C6F5)3, and the Lewis acidic additive B(C6F5)3 played a crucial role in achieving good reactivity. The reaction proceeds via CO2 reduction, C-C bond formation, and reduction. Water is the only byproduct of this environmentally friendly alternative for C-H methylation.
Article
Chemistry, Multidisciplinary
Dong Xu, Xiu Lin, Qi-Yuan Li, Shi-Nan Zhang, Si-Yuan Xia, Guang-Yao Zhai, Jie-Sheng Chen, Xin-Hao Li
Summary: This study successfully constructed a cascade catalyst that triggered the mild and cascade methylation of amines, achieving mass exchange between different catalysts through electron exchange and significantly improving the production of the desired product.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Shiqun Xiang, Weibin Fan, Wei Zhang, Yinghua Li, Shiwei Guo, Deguang Huang
Summary: A simple and green method for the synthesis of fused pyridines was developed using the [2 + 2 + 1 + 1] cycloaddition of ketones with an ammonium cation under a CO2 atmosphere. Monoethanolamine (MEA) was used as an additive to increase the solubility of CO2 in an aqueous solution. The products, exhibiting photosensitivity, show potential applications as organic optoelectronic materials, with a proposed reaction mechanism based on experimental studies.
Article
Chemistry, Multidisciplinary
Zhaofeng Gao, Jingwen Liu, Haizhou Huang, Huiling Geng, Mingxin Chang
Summary: The research reports on efforts to merge two asymmetric reductive amination reactions into a single-step transformation, utilizing specific catalyst and acid additives to successfully synthesize enantiopure secondary amine products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Inorganic & Nuclear
Zhi-Qiang Wang, Cheng-Hua Deng, Xiao Liu, Wen-Min Wang
Summary: In this study, a green-synthesis produced aluminum-based metal-organic framework (Al-MOF) material CAU-10pydc was used as a catalyst for CO2 formylation reaction. The results showed that CAU-10pydc could effectively catalyze the reaction of CO2 and N-methylaniline to N-methyl-N-phenylformamide under mild conditions. CAU-10pydc maintained its efficient catalytic performance after cyclic catalysis and exhibited stability. The universality of this catalyst was demonstrated through reactions with nine substrates. This work represents the first example of a highly effective Al-MOF catalyzing CO2 formylation reaction under green conditions.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Shuang-Shuang Ma, Rui Sun, Zi-Heng Zhang, Peng-Xin Guan, Jin-Qing Lin, Chun-Shan Li, Bao-Hua Xu
Summary: A novel half-sandwich phosphinesulfonate cobaltic complex was prepared and used for the chemoselective N,N-dimethylation of nitroaromatics. The catalytic activity could be modulated by using specific hydrosilanes.
Article
Chemistry, Multidisciplinary
Zhaozhuo Yu, Zhengyi Li, Lilong Zhang, Kaixun Zhu, Hongguo Wu, Hu Li, Song Yang
Summary: Chemocatalytic upgrading of CO2 to valuable chemicals and biofuels has drawn significant attention, with N-formylation of CO2 with an amine playing a crucial role in constructing N-containing linear and cyclic skeletons. A stable N-heterocyclic carbene-carboxyl adduct (NHC-CO2) was developed as a recyclable zwitterionic catalyst for efficient CO2 reductive upgrading, achieving remarkable yields of up to 98%. The introduced substituent on NHC-CO2 was found to impact its thermostability and nucleophilicity, directly influencing catalytic activity. Additionally, NHC-CO2 demonstrated the ability to supply CO2 through in situ decarboxylation at specific temperatures.
Article
Green & Sustainable Science & Technology
Zhengyi Li, Hu Li, Song Yang
Summary: This study successfully utilizes the carboxylate-functionalized zeolitic imidazolate framework (F-ZIF-90) as a heterogeneous catalyst for the reductive N-functionalization of various amines with CO2. The catalyst exhibits good catalytic performance, thermodynamic stability, and adsorption capacity towards CO2, leading to the high-yield production of N-formyl compounds. This strategy provides a new avenue for the development of heterogeneous catalysts for the reductive upgrading of CO2.
ADVANCED SUSTAINABLE SYSTEMS
(2022)
Article
Chemistry, Multidisciplinary
Ling Chen, Cheng Tang, Yan Jiao, Shi-Zhang Qiao
Summary: Tailoring the copper catalyst morphology by forming nanopyramids offers alternative routes to promote C-2 production, leading to improved C-C coupling behaviors due to the pyramidal effect on under-coordinated Cu (111) surface. This study utilized density functional theory calculations to investigate five polycrystalline Cu nanopyramids with various orientations, shapes, and exposing facets, and developed a new morphology design rule for efficient catalyst development based on the results of C-2 active site screening principle.
Review
Chemistry, Applied
Naina Sarki, Vishakha Goyal, Kishore Natte, Rajenahally V. Jagadeesh
Summary: C-methylation is a widely used chemical modification in life science molecules, with the magic methyl effect playing a key role in medicinal chemistry and drug discovery. Methanol as a convenient -CH3 source has become crucial for achieving sustainable and cost-effective methylation reactions.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Review
Chemistry, Multidisciplinary
Jian-Heng Ye, Tao Ju, He Huang, Li-Li Liao, Da-Gang Yu
Summary: Carbon dioxide is a valuable carbon resource in organic synthesis, but its utilization is challenging due to stability and inertness. Researchers have developed radical-type carboxylations and cyclizations using visible-light photoredox catalysis and copper catalysis. These strategies have expanded the scope of CO2 transformations and provided new methods for selective organic synthesis.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Chemistry, Multidisciplinary
John-Paul J. Bow, Valentina Adami, Agostino Marasco, Gaute Gronnevik, Dean A. Rivers, Guiseppe Alvaro, Patrick J. Riss
Summary: In this study, a method for isotopic labelling of hydantoins directly from CO2 was developed using trimethyl-lambda(5)-phosphine diiodide mediated carbonyl insertion. The method demonstrated high isolated yields and radiochemical yields, making it suitable for a wide range of substrates and for the synthesis of radiotracers in PET imaging facilities.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Koichi Nakaoka, Chao Guo, Yuta Saiki, Shin Furukawa, Tadashi Ema
Summary: In this study, TBAA and Cu(OAc)(2) were used as a binary catalytic system for the solvent-free N-formylation of amines with CO2 and PhSiH3. This catalysis not only synthesized enamines, aldehydes, and nitriles, but also formed C-H and C-N bonds, achieving a one-pot synthesis.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Kazuto Takaishi, Hiroyasu Kosugi, Ritsuki Nishimura, Yuya Yamada, Tadashi Ema
Summary: A pentanuclear zinc complex catalyzed the one-step C-methylenation of anilines and indoles with CO2 and phenylsilane to form diarylmethanes. The zinc-hydride complex generated in situ is proposed as the catalytically active species, with bis(silyl)acetal identified as a key intermediate in the reaction mechanism. Using aniline as a substrate, both C-methylenation and N-methylation were observed.
CHEMICAL COMMUNICATIONS
(2021)
Article
Multidisciplinary Sciences
Brian Fry, James F. Carter, Kaitlyn O'Mara
Summary: Despite differences in metabolism, eukaryotes have a common mitochondrial biochemistry. A high-resolution carbon isotope approach was used to investigate how this biochemistry supports overall metabolism. The study focused on carbon isotope cycling in animals and found contrasting patterns related to different metabolic life histories. The results provide insights into metabolism and metabolic strategies across the eukaryotic animal kingdom.
Article
Chemistry, Physical
Chi Fang, Chunlei Lu, Muhua Liu, Yiling Zhu, Yao Fu, Bo-Lin Lin
Article
Multidisciplinary Sciences
Hua Liu, Yi-Ling Zhu, Zhi Li
NATURE COMMUNICATIONS
(2019)
Article
Chemistry, Applied
Chunlei Lu, Zetian Qiu, Maojie Xuan, Yan Huang, Yongjia Lou, Yiling Zhu, Hao Shen, Bo-Lin Lin
ADVANCED SYNTHESIS & CATALYSIS
(2020)
Article
Chemistry, Multidisciplinary
Jingjing Xie, Pan Xu, Yiling Zhu, Jingyi Wang, Wan-Chen Cindy Lee, X. Peter Zhang
Summary: By optimizing the Co(II)-based metalloradical catalyst with a chiral ligand, a new catalytic radical process has been developed for asymmetric 1,4-C-H alkylation of diazoketones, leading to the construction of chiral cyclobutanone structures with high stereoselectivity. This process offers a mild and efficient method for the synthesis of enantioenriched cyclobutanones with potential applications in stereoselective organic synthesis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Xiaoxu Wang, Jing Ke, Yiling Zhu, Arghya Deb, Yijie Xu, X. Peter Zhang
Summary: A highly efficient catalytic method has been developed for asymmetric radical cyclopropanation of alkenes using Co(II)-based metalloradical catalysis, allowing for broad applicability to various substrates through fine-tuning of the synthesized chiral ligands. This new methodology provides access to valuable chiral heteroaryl cyclopropanes in high yields with excellent diastereoselectivities and enantioselectivities. Computational and experimental studies support a stepwise radical mechanism involving α- and γ-metalloalkyl radicals as key intermediates in the Co(II)-based olefin cyclopropanation.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Wan-Chen Cindy Lee, Jingyi Wang, Yiling Zhu, X. Peter Zhang
Summary: Asymmetric radical bicyclization processes using metalloradical catalysis have been developed to construct chiral chromanones and chromanes with fused cyclopropanes. Through optimization of the chiral amidoporphyrin ligand platform, a Co(II)-metalloradical system can activate different alkene functionalities under mild conditions for effective radical bicyclization, delivering desired products with high yields and excellent control of stereoselectivities. Computational and experimental studies reveal the stepwise radical mechanisms involved in the Co(II)-catalyzed bicyclization processes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)