Article
Chemistry, Multidisciplinary
Xinyu Zhang, Hui Wang, Lili Xie, Chenhui You, Xiaoyan Han, Zhiqiang Weng
Summary: An efficient synthesis protocol for 5-aryl-6-(trifluoromethyl)-2,3-dihydropyrazolo[1,2-a]pyrazol-1(5H)-one derivatives was developed via copper-catalyzed [3+2]-cycloaddition, with subsequent oxidation and nucleophilic substitution/aromatization providing a new approach to 4-trifluoromethylated pyrazol-1-yl propanoic acids. The transformation boasts a broad substrate scope and good functional group compatibility.
CHEMISTRY-AN ASIAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Huan Zhou, Li-Wen Fan, Yang-Qing Ren, Li-Lei Wang, Chang-Jiang Yang, Qiang-Shuai Gu, Zhong-Liang Li, Xin-Yuan Liu
Summary: The copper-catalyzed enantioselective radical difunctionalization of alkenes provides a convenient method for synthesizing alpha-chiral alkyl phosphorus compounds. The main challenge lies in controlling the chemoselectivity due to the generation of P-centered radicals from the P-H-type reagent. This study introduces a highly chemo- and enantioselective radical 1,2-carbophosphonylation of styrenes by using dialkyl phosphites and an anionic chiral N,N,N-ligand as key components.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Kun-Quan Chen, He Sheng, Qiang Liu, Pan-Lin Shao, Xiang-Yu Chen
Summary: In recent years, NHC-catalyzed radical reactions have been gaining attention for their potential to create new activation modes previously inaccessible. Further research and understanding of this emerging area is warranted to explore its synthetic techniques and advantages.
SCIENCE CHINA-CHEMISTRY
(2021)
Article
Chemistry, Organic
Kosuke Yasui, Miharu Kamitani, Hayato Fujimoto, Mamoru Tobisu
Summary: This study reports on the N-heterocyclic carbene (NHC)-catalyzed Truce-Smiles rearrangement of aniline derivatives, where an unactivated C(aryl)-N bond is cleaved to form a new C(aryl)-C bond. The key to the success of this reaction lies in the utilization of highly nucleophilic NFIC, which enables the formation of a highly nucleophilic ylide intermediate generated from an alpha,beta-unsaturated amide.
Article
Chemistry, Multidisciplinary
Sota Akiyama, Natsuki Oyama, Tsubura Endo, Koji Kubota, Hajime Ito
Summary: The first catalytic intermolecular 1,2-alkylborylation reaction via a radical-relay mechanism was reported in this study, involving unactivated olefins, bis(pinacolato)diboron, and an alkyl electrophile. Overcoming the challenge of competing boryl substitution of the alkyl electrophile was achieved by using electronically or sterically demanding alkyl electrophiles, resulting in the simultaneous and highly regioselective introduction of various alkyl and boron groups.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Juan Du, Xing Wang, Hongling Wang, Jinhu Wei, Xuan Huang, Jun Song, Junmin Zhang
Summary: A novel Pd-catalyzed reaction method is described in this study, which can be used to synthesize a diverse range of bioactive oxindole derivatives.
Article
Chemistry, Multidisciplinary
Qing-Yun Fang, Jie Han, Mingzhe Qin, Weipeng Li, Chengjian Zhu, Jin Xie
Summary: Reported here is a three-component 1,2-difunctionalization reaction of alkenes, unactivated alkyl bromides, and nucleophiles (e.g., amines and indoles) using a trinuclear gold catalyst [Au-3(tppm)(2)](OTf)(3). This reaction enables facile 1,2-aminoalkylation and 1,2-alkylarylation and exhibits a broad reaction scope and excellent functional group compatibility (>100 examples with up to 96% yield). It also provides a robust formal [2+2+1] cyclization strategy for the concise construction of pyrrolidine skeletons under mild reaction conditions. Mechanistic studies support an inner-sphere single electron transfer pathway for the successful cleavage of inert C-Br bonds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Wei Wu, Shunli Wen, Xinyu Zhang, Qi Lin, Zhiqiang Weng
Summary: A highly efficient and regioselective synthesis of highly substituted 2-trifluoromethyl pyrrole derivatives is reported via a silver-catalyzed cyclization of vinyl azides with ethyl 4,4,4-trifluoro-3-oxobutanoate. Various types of alpha-(heteo)aryl, alkyl, alpha-aryl, and alpha,beta-disubstituted vinyl azides can participate in this transformation. The proposed reaction mechanism involves the addition of in situ generated 2H-azirine to the diketone species, followed by intramolecular addition, N-C-1 cleavage, and elimination.
Article
Chemistry, Organic
Gwilherm Evano, Cedric Theunissen
Summary: Copper is an efficient and attractive metal for catalysis. Copper complexes are utilized to catalyze various reactions, including those involving radicals, due to their availability, low cost, and limited toxicity. This account summarizes our contributions to the catalysis of radical reactions from organic halides with copper complexes.
Article
Chemistry, Physical
Huan Zhou, Zhong-Liang Li, Qiang-Shuai Gu, Xin-Yuan Liu
Summary: Transition-metal-catalyzed asymmetric C-(sp(3))-C cross-coupling is an efficient method for the rapid synthesis of enantioenriched molecules. Chiral copper catalysts have been designed to promote a variety of asymmetric radical C(sp(3))-C cross-coupling reactions with high efficiency and enantioselectivity. The key to success lies in the design of chiral ligands to initiate the reaction and achieve enantiocontrol over the highly reactive prochiral alkyl radical species.
Article
Chemistry, Physical
Fengqian Zhao, Jian-Xing Xu, Fu-Peng Wu, Xiao-Feng Wu
Summary: This communication describes a copper-catalyzed selectivity-reversed borocarbonylation. In the presence of CuOAc/BuPAd2 catalytic system, a series of unactivated terminal alkenes were transformed into β-boryl ketones in moderate yields, using sterically hindered alkyl bromides as the electrophiles.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Junki Matsumoto, Yusei Nakashima, Takashi Nishikata
Summary: Here, an efficient method using transition metal catalysts to control the reaction of alpha-bromocarbonyls with a styrene moiety is reported. The iron catalyst leads to the formation of cyclic compounds with a C-C double bond, while the copper catalyst produces halogenated cyclic compounds.
Article
Chemistry, Physical
Tian-Tian Li, Ying Cheng, Wen-Jing Xiao, De-Qing Shi, Jia-Rong Chen
Summary: A copper-catalyzed enantioselective three-component radical relay 1,2-alkylesterification of 1,3-dienes using cycloalkyl hydroperoxides and carboxylic acids was reported. This protocol features broad substrate scope and good functional group tolerance with respect to each component, providing practical access to a variety of distally keto-functionalized allylic esters with high enantioselectivity under mild and redox-neutral conditions.
Article
Chemistry, Multidisciplinary
Robert D. Riley, Blake S. N. Huchenski, Karlee L. Bamford, Alexander W. H. Speed
Summary: This study demonstrates that diazaphospholene hydrides can be regenerated by the combination of phenylsilane and alkali metal salts, enabling catalytic radical reactions of aryl iodides. The method is not only applicable to aryl iodides, but can also be extended to aryl bromides, which benefit from visible light irradiation. Additionally, intermolecular radical hydroarylation reactions with arenes, thiophenes, and a pyridine have been successfully achieved.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Roel F. J. Epping, David Vesseur, Minghui Zhou, Bas de Bruin
Summary: Discovered in the 1970s as organometallic curiosities, carbene radicals have become essential in modern homogeneous catalysis. These radicals exhibit nucleophilic reactivity different from electrophilic Fischer carbenes. The successful catalytic application of carbene radicals has led to the synthesis of diverse carbon and heterocyclic compounds. This Perspective provides an overview of the coordination chemistry, reactivity, and catalytic application of carbene radicals using transition metal complexes and catalysts since 2011.
Article
Chemistry, Organic
Faiza Diaba, Gisela Trenchs
Summary: The first violet light-mediated synthesis of gamma- and delta-lactams from N-alkenyl trichloroacetamides is reported in this paper. The reactions are conducted in tetrahydrofuran or 2-methyltetrahydrofuran as the sole solvent without catalysts or additives, under non-anhydrous conditions in an air atmosphere where the solvent serves as the radical initiator.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Feroze Hussain, Sajjad Ahmed, Ashiq Hussain Padder, Qazi Naveed Ahmed
Summary: This study reports a novel and efficient one-pot synthesis method for mixed phosphorotrithioates, which does not require supplementary additives and shows broad applicability.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Hyunjin Oh, Ikyon Kim
Summary: A new 1,2,4-triazole-pyrrolo[1,2-a]pyrazine hybrid system, 6-acylpyrrolo[1,2-a][1,2,4]triazolo[5,1-c]pyrazine, was synthesized using a catalyst-free method. This method involved sequential exposure of pyrrole-2-carbonitrile-derived substrates to DMF-DMA and acyl hydrazide, resulting in the formation of acylated pyrazine and 1,2,4-triazole rings, enabling the installation of various substituents at specific positions on the core skeleton.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Ming Yan, Si-fan Wang, Yong-po Zhang, Jin-zhong Zhao, Zhuo Tang, Guang-xun Li
Summary: Here we developed an efficient photocatalytic approach for the convenient preparation of sulfinamides. The reaction allows for the gram-scale preparation of sulfinamides and the one-pot synthesis of various sulfonyl amides.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Farzaneh Bandehali-Naeini, Zahra Tanbakouchian, Noushin Farajinia-Lehi, Nicolas Mayer, Morteza Shiri, Martin Breugst
Summary: Two tandem catalytic systems were developed for the synthesis of novel 3,4-disubstituted maleimides using the same Ugi adducts. Different maleimide structures can be synthesized using either Pd or Cu catalysis.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Tanya Raghava, Anjan Chattopadhyay, Subhadeep Banerjee, Nivedita Sarkar
Summary: Amine substitution of two ortho fluorine atoms of tetrafluoroterephthalonitrile through SNAr chemistry is easily achievable. But further fluorine substitution is only possible under forcing conditions, yielding valuable fluorophores for bioimaging.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Review
Chemistry, Organic
Anju Chadha, Santosh Kumar Padhi, Selvaraj Stella, Sowmyalakshmi Venkataraman, Thangavelu Saravanan
Summary: Alcohol dehydrogenases are enzymes that use cofactors for oxidation or reduction reactions of alcohols or carbonyl compounds. They are utilized in green chemistry and have applications in the production of pharmaceuticals. Recombinant enzymes have solved the challenge of producing purified enzymes in large quantities. Engineered alcohol dehydrogenases have been used in asymmetric synthesis in industry. Various methods have been established for regenerating expensive cofactors to make the enzymatic process more efficient and economically viable.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)