Article
Chemistry, Organic
De Wang, Zefeng Song, Jianyu Zhang, Tao Xu
Summary: A novel remote delta methylene C(sp(3))-H functionalization was discovered, catalyzed by an organophosphine through alkyne isomerization/conjugate addition cascade without the need for a classical electron-withdrawing group. The process, under only 10 mol% of PMe2Ph with a catalytic proton shuttle, successfully produced a large group of functionalized products with good diastereoselectivity. Mechanistic studies and fluorescence properties of the conjugated polyene products were investigated in detail.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Review
Chemistry, Organic
Asha Joshi, De Saroj Ranjan
Summary: Transition-metal-catalyzed chelation assisted C(sp(2)/sp(3))-H bond arylation using diaryliodonium salts as coupling partners is an efficient method to achieve molecular diversity. By introducing aryl or biaryl derivatives, it can play an important role in industries, agriculture, medicinal, and material science.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Yuhang Yang, Weiwei Gao, Yongqiang Wang, Xiaodong Wang, Fei Cao, Tao Shi, Zhen Wang
Summary: This article reviews the main progress of copper-promoted inert C(sp(3))-H functionalization in establishing different types of bonds, presenting reaction characteristics, proposed mechanisms, and future development trends in this field.
Article
Chemistry, Organic
Xu Wang, Yuting Xue, Weinan Hu, Linlin Shi, Xinju Zhu, Xin-Qi Hao, Mao-Ping Song
Summary: A copper-catalyzed delta-regioselective C(sp(3))-H heteroarylation of N-fluorosulfonamides has been developed, providing a practical strategy for the functionalization of heteroarenes and amides via forging a C(sp(3))-C(sp(2)) bond. A broad range of heteroarenes were well tolerated and reacted with various N-fluorosulfonamides to give the corresponding heteroarylated amides in good yields. Notably, all types of delta-C(sp(3))-H bonds in the N-fluorosulfonamides could be regioselectively activated through the 1,5-HAT process.
Article
Chemistry, Organic
Naveen Kumar Maurya, Suman Yadav, Dhananjay Chaudhary, Dharmendra Kumar, Km Ishu, Malleswara Rao Kuram
Summary: In this study, cyclic diaryliodonium salts were developed as biarylating agents for C(sp3)-H functionalization, using 8-methyl quinoline as the intrinsic directing group. The oxidant-free reaction resulted in a wide range of biarylated products with iodo functionality, which can be further functionalized. Furthermore, intramolecular C(sp3)-H functionalization under palladium-catalyzed conditions produced fluorene derivatives with excellent yields.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Lukas Janecky, Athanasios Markos, Blanka Klepetar, Petr Beier
Summary: 4-Aryl-5-allyl-N-fluoroalkyl-1,2,3-triazoles were synthesized through a three-component reaction of fluoroalkyl azides, copper acetylides, and allyl halides. These compounds underwent aluminum halide-mediated transformation to N-(4-halo-2-aryl-cyclopentenyl) imidoyl halides by cyclization of vinyl cation intermediates, followed by halide capture. The cyclic products could be further utilized for the synthesis of N-alkenyl amides, amidines, isoquinolines, and tetrazoles, or for the subsequent modification of the cyclopentene ring.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Hui Shu, Mengjie Guo, Machongyang Wang, Shuibo Fan, Mingbo Zhou, Ling Xu, Yutao Rao, Atsuhiro Osuka, Jianxin Song
Summary: In this study, a rhodium-catalyzed C-H/N-H [5 + 2] annulation reaction between 8-(pyrrol-2-yl)-appended boron-complexed dipyrromethenes (BODIPYs) and internal alkynes was established to synthesize a series of azepine-fused BODIPYs with good yields and excellent regioselectivity, using the pyrrol-2-yl unit as a rare directing group. The formation of a RhI intermediate indicates the involvement of a RhI/RhIII catalytic process. Importantly, the [5 + 2] C-H annulation is demonstrated as a concise strategy for modifying the optical properties of BODIPY.
Article
Chemistry, Multidisciplinary
Yin-Xia Wang, Feng-Ping Zhang, Hao Chen, Yue Li, Jiang-Fei Li, Mengchun Ye
Summary: Enantioselective Ni-catalyzed C(sp(3))-H bond activation was achieved using a phosphine oxide-ligated Ni-Al bimetallic catalyst, leading to the synthesis of a series of chiral N-containing heterocycles in good yields and high enantioselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Arghadip Ghosh, Nicolas Grimblat, Somratan Sau, Arijit Saha, Vincent Gandon, Akhila K. Sahoo
Summary: This article presents a Pd-(II)-catalyzed direct difunctionalization of two C-(sp(3))-H bonds of aliphatic carboxylic acid derivatives using bifunctional reagents (BFRs) of the 2-iodobenzoic acid series. Various directing groups, ligands, bases, and co-oxidants are employed to facilitate the reaction, leading to the formation of benzo-fused peripheral-substituted caprolactones. Mechanistic studies provide insights into the crucial steps involved in the transformation. The versatility of the complex molecular entities is also showcased.
Article
Chemistry, Multidisciplinary
Sean M. Treacy, Tomislav Rovis
Summary: By utilizing catalytic CuCl2, various feedstock chemicals can be functionalized through the coupling of unactivated C(sp(3))-H bonds with electron-deficient olefins. This reaction, enabled by Ligand-to-Metal Charge Transfer (LMCT), generates a chlorine radical capable of abstracting strong electron-rich C(sp(3))-H bonds. The protocol offers a simple operation and atom economical approach to generate a highly active hydrogen atom transfer reagent.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Multidisciplinary Sciences
Rong-Hua Wang, Wei-Wei Xu, Hongli Wu, Yue Li, Jiang-Fei Li, Tao Zhang, Genping Huang, Mengchun Ye
Summary: In this study, we report a new phosphine oxide-ligated Ni-Al bimetallic catalyst that can efficiently activate secondary benzylic C-H bonds via 4-membered nickelacycles, leading to the synthesis of high-yield α,β-unsaturated γ-lactams.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Organic
He Zhang, Dandan Yang, Xiao-Fang Zhao, Jun-Long Niu, Mao-Ping Song
Summary: This article describes an efficient method for cobalt-catalyzed C(sp(3))-H bond functionalization to synthesize indole derivatives, achieved through sequential C-H activation. The method offers mild reaction conditions, low cost, and good functional group tolerance.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Mu-Jia Luo, Gui-Fen Lv, Jing-Hao Qin, Chong-Hui Xu, Yang Li, Jin-Heng Li
Summary: This study presents a rhodium-catalyzed electrochemical reaction for the selective synthesis of structurally diverse hexasubstituted arenes. The method demonstrates excellent selectivity and high atom economy.
Article
Chemistry, Multidisciplinary
Mu-Jia Luo, Gui-Fen Lv, Jing-Hao Qin, Chong-Hui Xu, Yang Li, Jin-Heng Li
Summary: A cooperative rhodium-catalyzed electrochemical 1,3-butadiyne [2 + 2 + 2] cyclotrimerization is presented, which selectively produces hexasubstituted arenes. The method features high selectivity, good functional group tolerance, and high atom economy.
Article
Chemistry, Multidisciplinary
Shuang Liu, Zhe Zhuang, Jennifer X. Qiao, Kap-Sun Yeung, Shun Su, Emily C. Cherney, Zheming Ruan, William R. Ewing, Michael A. Poss, Jin-Quan Yu
Summary: A novel catalytic system was reported for the intramolecular gamma-C-H amination of aliphatic amides derived from amino acids, enabling the convenient synthesis of lactams, isoindolinones, and 2-imidazolidinones. This protocol demonstrates the utility of utilizing N-acyl amino acids as directing groups and cyclization partners, tert-butyl hydrogen peroxide as the sole oxidant, and a broad substrate scope for the construction of important structural cores of medicinal compounds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Yaru Niu, Chengyao Kimmy Cao, Chenxin Ge, Hongmei Qu, Chao Chen
Summary: In this study, a simple and efficient method for directly introducing a chlorodifluoroethyl group into aromatic molecules of various aromatic amides is reported. A new 2-chloro,2,2-difluoroethyl(mesityl)iodonium salt (CDFI) is used in this method. Furthermore, the chlorodifluoroethyl compounds can be smoothly converted into difluorovinyl compounds and serve as a stable source of difluorovinyl compounds with HCl-mask.
CHINESE CHEMICAL LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Song Zou, Zeyu Zhang, Chao Chen, Chanjuan Xi
Summary: This study achieved the formal [4 + 2] annulation of styrene oxides with alkynes catalyzed by MeOTf, resulting in polysubstituted naphthalenes with sequential electrophilic cyclization/ring expansion. The reaction showed high regioselectivity with satisfactory yields and could be carried out on gram scale.
CHINESE CHEMICAL LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Yixin Zhang, Jinfeng Zhao, Dawei Yang, Baomin Wang, Yuhan Zhou, Junhu Wang, Hui Chen, Tao Mei, Shengfa Ye, Jingping Qu
Summary: Researchers have discovered a well-described multi-iron nitrido model complex with excellent reactivity towards converting hydrogen and nitrogen gas into high-yield ammonia under ambient conditions. These studies have overcome the previous challenges of converting nitrides to ammonia and provided new insights.
Article
Chemistry, Multidisciplinary
Yaxing Wu, Chao Wu, Fei Wang, Chao Chen
Summary: A [2 + 2 + 1] annulation protocol has been developed for the modular synthesis of 2,4-disubstituted thiophenes/selenophenes, showing excellent regioselectivity. Catalyzed by copper salt, the reactions utilize elemental sulfur and selenium as the chalcogen source. Mechanistic studies indicate that the process is initiated by a trisulfur radical anion detected using EPR.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Organic
Jun Zhou, Zhiyuan Bao, Panpan Wu, Chao Chen
Summary: Diaryliodonium salts derived from gemfibrozil and gemfibrozil methyl ester were synthesized with good regioselectivity and successfully utilized in various derivatization reactions.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Multidisciplinary
Faju Li, Linhong Long, Yan-Mei He, Zeyu Li, Hui Chen, Qing-Hua Fan
Summary: A unique family of chiral macrocyclic ligands with a tunable saddle-shaped cavity is described. Using their manganese(I) complexes, the first example of earth-abundant transition metal-catalyzed asymmetric formal anti-Markovnikov hydroamination of allylic alcohols was achieved, providing a practical access to synthetically important chiral gamma-amino alcohols. The study revealed the remarkable role of the macrocyclic framework in the reaction process.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Shaohong Wang, Pengchen Ma, Sason Shaik, Hui Chen
Summary: Valence-inverted reactivity (VIR) is discovered through high-level computations of excited states of Ni(II) complexes that are generated by triplet energy transfer, and it plays a significant role in C-H bond activation and cross-coupling reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Jiarui Lu, Wenzhen Lai, Hui Chen
Summary: Through QM/MM modeling, it was discovered that C(sp(3))-H beta-hydroxylation in the diiron hydroxylase CmlA occurs through traceless amine-assisted O-2 activation. This unique mode of O-2 activation generates a diferric (Fe2O2)-O-III species instead of the conventional diferryl (Fe22O2)-O-IV species, resulting in a different C(sp(3))-H hydroxylation mechanism compared to other diiron hydroxylases. This substrate-modulated O-2 activation in CmlA has significant implications for understanding the mechanism of other diiron hydroxylases with similar amine groups adjacent to C-H bonds. Furthermore, the adapted coordination environment of the diiron cofactor upon O-2 binding in CmlA opens up possibilities for O-2 activation in non-heme diiron enzymes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Zhiyuan Bao, Chao Chen
Summary: An efficient method for the synthesis of multi-substituted cyclic imides was developed using cyanoesters and diaryliodonium salts. This method involves a cascade of N-arylation-acylation and rearrangement reactions, producing the desired heterocycles in high yields. The method has a broad substrate scope, excellent functional group compatibility, and can be extended to fused cyclic imides.
CHINESE CHEMICAL LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Zelong Wang, Silin Chen, Chao Chen, Yunhui Yang, Congyang Wang
Summary: Earth-abundant transition metal catalysis has been developed as a viable substitute for noble transition metal catalysis in hydrogenation reactions. However, the hydrogenation of thioamides using earth-abundant transition metals has not been reported due to catalyst poisoning by sulfur-containing molecules. In this study, we successfully achieved manganese-catalyzed hydrogenative desulfurization of thioamides to amines or imines by employing MnBr(CO)(5) instead of commonly-used pincer-manganese catalysts, along with NEt3 and CuBr. This reaction demonstrated excellent selectivity in breaking the C=S bond of thioamides, unlike the only known Ru-catalyzed hydrogenation of thioamides, and it exhibited unprecedented chemo-selectivity towards vulnerable functional groups.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yaxing Wu, Yunchen Jiang, Fei Wang, Bin Wang, Chao Chen
Summary: This article introduces the emerging application of the isoperfluoropropyl group (i-C3F7) in pharmaceuticals, agrichemicals, and functional materials. By inventing a hypervalent-iodine-based reagent-PFPI reagent, the efficient isoperfluoropropylation of aromatic C-H bonds is achieved through an Ag-X coupling process. The PFPI reagent is demonstrated to activate without catalysts or additives in the synthesis of isoperfluoropropylated electron-rich heterocycles, and its activity under photoredox catalysis is shown in the synthesis of isoperfluoropropylated non-activated arenes. The mechanistic pathway in the photoredox reactions is revealed through detailed experiments and DFT calculations, and the unique conformation of i-C3F7 involving intramolecular hydrogen bond in products is investigated.
COMMUNICATIONS CHEMISTRY
(2023)
Review
Chemistry, Organic
Chen Silin, Yang Yunhui, Chen Chao, Wang Congyang
Summary: In the past two decades, transition-metal-catalyzed keto carbonyl-directed C-H bond activation has been extensively studied, with noble metals like ruthenium, rhodium, palladium, and iridium as catalysts, as well as inexpensive 3d metals such as manganese, iron, and cobalt. This review summarizes the recent advances in transition-metal-catalyzed keto carbonyl-directed C-H bond functionalization reactions from 2014 to 2021, including various reaction categories such as alkylation, alkenylation, amidation, arylation, cyclization, and more.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Chengyao Kimmy Cao, Niu Yaru, Jiang Yunchen, Qu Hongmei, Chen Chao
Summary: In this study, a new method for synthesizing difluoroethyl compounds was developed through a palladium-catalyzed chlorodifluoroethylation reaction. Furthermore, difluorovinylated acetanilide products were obtained through an elimination reaction.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Li-Hui Mou, Yao Li, Gong-Ping Wei, Zi-Yu Li, Qing-Yu Liu, Hui Chen, Sheng-Gui He
Summary: This study investigates a likely reaction pathway for the N-C coupling of N-2 and CH4 mediated by heteronuclear metal cluster anions CoTaC2-, which involves the dissociative adsorption of N-2 and the activation of CH4 to construct the N-C bond. The study proposes a novel N-t triggering strategy using metal clusters, providing a new idea for the direct synthesis of N-containing compounds.
Article
Chemistry, Organic
Song Zou, Xuewei Luo, Chao Chen, Chanjuan Xi
Summary: A photoredox-catalyzed three-component fluorodifluoroacetylation of aromatic alkenes is reported, showcasing a broad substrate scope and tolerance towards functional groups. One advantage of the reaction is the utilization of a nucleophilic fluoride source and a general difluoroacetylation reagent for the fluorodifluoroacetylation of alkenes.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
