Article
Chemistry, Multidisciplinary
Wei Yi, Weijie Chen, Huiying Xu, Kaifeng Chen, Xiuhua Zhong, Zhi Zhou
Summary: Transition metal-catalyzed C-H functionalization is a powerful synthetic tool for accessing valuable structural motifs. However, remote C-H activation, such as y-C(sp3)-H and meta-C(sp2)-H versions, is less explored and more challenging than ortho-C(sp2)-H activation. In this study, by fine-tuning the characteristics of osmium bond generated through phenylpyridine scaffold-mediated ortho-C-H activation/C,N-bidentate coordination, highly efficient and selective intramolecular y-C(sp3)-H amidation and intermolecular meta-C(sp2)-H alkylation were achieved. The observed selectivity and reaction pathways were clarified through experimental and computational mechanistic studies. This work provides valuable insights for the future development of C-H functionalizations mediated by transition metals, especially osmium.
CELL REPORTS PHYSICAL SCIENCE
(2023)
Article
Chemistry, Applied
Liang-Neng Wang, Pan-Ting Tang, Ming Li, Jia-Wei Li, Yue-Jin Liu, Ming-Hua Zeng
Summary: The combination of 1,3-diketone and amino acid ligands is essential for the ruthenium-catalyzed C(sp(2))-H arylation of dialkyl phosphines, providing a direct access to aryl-substituted dialkyl phosphine ligands. Mechanistic studies showed that the 1,3-diketone promoted the process of oxidative addition of a cycloruthenium intermediate, and some modified CyJohnPhos ligands exhibited highly catalytic activity in palladium catalyzed C-N bond formation.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Tatsuhiro Uchikura, Sotaro Kato, Yudai Makino, Megumi J. J. Fujikawa, Masahiro Yamanaka, Takahiko Akiyama
Summary: Desymmetrization is a crucial technique for synthesizing chiral compounds, especially chiral biaryls. This study presents an enantioselective synthesis of axially chiral biaryls through desymmetrization using chiral palladium phosphate as the catalyst for C(sp(3))-H activation. Mechanistic investigations reveal that C-H activation plays a crucial role in determining the rate and enantiomeric selectivity. To the best of our knowledge, this is the first report on the asymmetric desymmetrization of axially chiral compounds via C(sp(3))-H activation.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Amal Benzai, Fazia Derridj, Henri Doucet, Jean-Francois Soule
Summary: The study reports a Pd- or Ru-catalyzed arylation reaction that allows for the ortho-arylation of the aryl unit of 2-arylpyrazines with high regioselectivity and applicability to various substituted pyrazine compounds. Experimental results demonstrate that even pyrazines with 2,3-diphenyl substitution can yield the desired arylated product.
Article
Chemistry, Multidisciplinary
Yunhe Jin, Qingqing Zhang, Lifang Wang, Xinyao Wang, Changgong Meng, Chunying Duan
Summary: The iron-catalysed photoredox system reported in this study enables the transformation of light alkanes into C-N and C-C bonds under ambient temperature, demonstrating high catalytic efficiency, mild conditions, and convenience in purification and scaling up. The system is sustainable, convenient, and environmentally friendly, with potential applications in high-value-added transformations of natural alkanes.
Article
Chemistry, Physical
Peng Zhou, Yu Chen, Zuowei Xie
Summary: In this study, a highly efficient iron-catalyzed method for the 4/5-fold cage B-H methylation/arylation of carboranes was developed without the need for noble transition metal catalysts. The reaction used organo-aluminum compounds as alkylation/arylation reagents and diethyl oxalate as an inexpensive oxidant, resulting in the synthesis of various compounds with good yields. This method represents an alternative strategy for the catalytic selective polyfunctionalization of carboranes via base metal catalysis.
Article
Chemistry, Physical
Peng Zhou, Yu Chen, Zuowei Xie
Summary: This paper reports a highly efficient iron-catalyzed, silver-free B-H methylation/arylation reaction of carboranes using organoaluminum compounds as reagents, leading to the synthesis of various substituted carboranes with excellent yields. This method allows for easy gram-scale synthesis and the proposed reaction mechanism provides insight into the process.
Article
Chemistry, Organic
Katrina Mackey, David J. Jones, Leticia M. Pardo, Gerard P. McGlacken
Summary: Utilizing a cheap and bench-stable quinoline ligand can overcome the challenges in synthesizing dibenzofurans via C-H functionalization, enabling high-yield synthesis. Dibenzofurans are important motifs in natural products and compounds with wide biological activity.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Xian-Chao Cui, Hu Zhang, Yi-Ping Wang, Jian-Ping Qu, Yan-Biao Kang
Summary: In this study, we report a new photocatalytic method for the 2- or 4-pyridylation of compounds containing O, N, or S groups, using the organic photoreductant CBZ6 and sulfoxides or sulfides as HAT reagents. This is the first base-free version of the alpha-C-H 2-/4-pyridylation of compounds containing ethers, amines, or thioethers.
Article
Chemistry, Multidisciplinary
Takeshi Yatabe, Tamon Tome, Yukina Takahashi, Takahiro Matsumoto, Ki-Seok Yoon, Hidetaka Nakai, Seiji Ogo
Summary: This study presents the first example of C-H arylation of benzene under mild conditions using H-2 as an electron source {with turnover numbers (TONs) of 0.7-2.0 for 24 hours}. The reaction relies on a Rh-based electron storage catalyst, operates at room temperature and in aqueous solution, and effectively suppresses unwanted side reactions by rendering H-2 inactive during the radical transfer step.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Torben Rogge, Thomas Mueller, Hendrik Simon, Xiaoyan Hou, Simon Wagschal, Diego Broggini, Lutz Ackermann
Summary: A triazole-directed direct C-H arylation of arenes with electron-deficient aryl halides or pyrimidyl chloride was achieved through ruthenium catalysis. This strategy provides a simple and environmentally friendly access to highly functionalized hetarenes, avoiding the use of strong organometallic bases. Detailed studies revealed a significant impact of the phosphine ligand, enabling the reaction to exhibit excellent levels of chemo- and position selectivity.
Article
Chemistry, Organic
Smruti Ranjan Mohanty, Namrata Prusty, Tanmayee Nanda, Shyam Kumar Banjare, Ponneri C. Ravikumar
Summary: In this study, the ruthenium-catalyzed regioselective sp2(C-H) monoalkenylation of N-arylpyridones was demonstrated, where the pyridone served as a weakly coordinating directing group. Importantly, this methodology was effectively applied to the synthesis of various drug analogues, with high yields up to 93%. HRMS analysis also revealed the presence of a six-membered ruthenium complex.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Applied
Liangliang Song, Gerardo M. Ojeda-Carralero, Divyaakshar Parmar, David A. Gonzalez-Martinez, Luc Van Meervelt, Johan Van Der Eycken, Jan Goeman, Daniel G. Rivera, Erik V. Van der Eycken
Summary: This report presents a ruthenium-catalyzed C-H activation/annulation process that can selectively modify the peptide backbone to produce functionalized isoquinolone scaffolds with high regioselectivity in a rapid and step-economical manner. The method allows for the production of fluorescent peptides, peptide conjugates with drugs, natural products, and other peptide fragments, providing a chemical approach for constructing novel peptide-pharmacophore conjugates.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Paul L. Kress, Shengjie Zhang, Yicheng Wang, Volkan Cinar, Cynthia M. Friend, E. Charles H. Sykes, Matthew M. Montemore
Summary: Single-atom catalysts have limitations in facilitating reactions that require multiple adjacent sites. This study introduces trimetallic dual-atom alloys as a new class of catalysts with desirable reactivity. Experimental evidence shows that Pt-Cr sites in Ag(111) can catalyze the conversion of ethanol, while PtAg and CrAg are unreactive. The discovery of thermodynamically favorable dual-atom alloy sites opens up new possibilities for creating materials with enhanced chemical reactivity beyond the single-atom paradigm.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Oleg V. Khazipov, Konstantin E. Shepelenko, Safarmurod B. Soliev, Ksenia A. Nikolaeva, Victor M. Chernyshev, Valentine P. Ananikov
Summary: This article presents a new efficient method for the C(2)-H arylation of (benz)imidazoles and (benz)oxazoles with aryl chlorides and aryl bromides under Ni/NHC catalysis, offering a user-friendly alternative to toxic phosphine ligands or unstable catalysts. By mapping a competitive picture of catalyst dynamics, a highly efficient catalytic system can be built under simple conditions for stabilization of catalytically active species.
Article
Chemistry, Organic
Fuying Zhu, Yamei Lin
Summary: In this study, a low-metal iron-supported catalyst (Fe20/NC-Mg) was reported for the efficient synthesis of quinoxaline compounds, using water as a solvent and without additional bases. The synergistic effect of FeNx site and Mg (OH)2 nanorods in the catalyst played a key role in achieving high yields (82-91%) in 16 examples. The gram-level synthesis and reusability of the catalysts after four cycles demonstrated its industrial application potential.
Article
Chemistry, Organic
Mikhail Kozlov, Alexey Tyurin, Andrey Dmitrenok, Vyacheslav Rusak, Aleksander Fedorov, Igor Zavarzin, Yulia Volkova
Summary: This study presents a novel and practical synthesis method for phosphorus-substituted 1,3,4-thiadiazolines using phosphorylthioformic acid hydrazides and ketones. The protocol demonstrates operational simplicity, availability of reagents, and tolerance towards different functional groups.
Article
Chemistry, Organic
Jisna Jose, Thomas Mathew
Summary: 2-Cyclopentenone and its derivatives are highly esteemed synthetic intermediates with exceptional utility in organic synthesis. They are favored structural motifs in numerous pharmaceutical drugs and natural products, highlighting their significance. The review discusses the various methods used to synthesize cyclopentenones from 2016 to 2023.