Article
Chemistry, Multidisciplinary
Ze-Jie Lv, Wei Liu, Wen-Xiong Zhang
Summary: As key intermediates in metal-promoted/catalyzed C-C bond coupling reactions of nitriles and alkynes, azametallacyclopentadienes, M(N=CR1-CR2=CR3), are an important class of azametallacycles. Research on their solid-state structures, intrinsic reactivity, and synthetic application was limited until the beginning of this century when they were found to have applications in the synthesis of heterocycles. Since then, various complexes with this motif have been isolated and characterized, including rare-earth azametallacyclopentadienes which show high reactivity towards unsaturated molecules.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Lin-Jun Qi, Cui-Ting Li, Zheng-Qi Huang, Jia-Tian Jiang, Xin-Qi Zhu, Xin Lu, Long-Wu Ye
Summary: The study presents a novel copper-catalyzed asymmetric formal annulation reaction, which can synthesize a range of chiral oxygen-heterocycles via carbonyl ylides with excellent enantioselectivity and yields.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Applied
Shan-Shan Zhu, Heng Li, Rong Fu, Wen-Juan Hao, Shu-Liang Wang, Shu-Jiang Tu, Bo Jiang
Summary: The Lewis acid-catalyzed tricyclization method enables the efficient synthesis of rotationally hindered tribenzo[a,c,j]xanthenes, allowing scission/recombination of C-C triple bonds with good stereoselectivity and substituent compatibility.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Biochemistry & Molecular Biology
Lucia Veltri, Roberta Amuso, Marzia Petrilli, Corrado Cuocci, Maria A. Chiacchio, Paola Vitale, Bartolo Gabriele
Summary: A straightforward method for the synthesis of new polycyclic heterocycles 1H-benzo[4,5]imidazo[1,2-c][1,3]oxazin-1-ones through ZnCl2-promoted deprotective 6-endo-dig heterocyclization of N-Boc-2-alkynylbenzimidazoles has been developed. The zinc center plays a dual role in this reaction. The structure of representative products has been confirmed by X-ray diffraction analysis.
Article
Chemistry, Organic
Dinesh S. Barak, Dipak J. Dahatonde, Sanjay Batra
Summary: A metal- and photoredox-catalyst free unified approach for the synthesis of azole-fused quinolines via annulation reaction between substituted 5/2-amino-N-phenyl azoles and alkynes in the presence of tert-butyl nitrite (t-BuONO) in acetonitrile is reported. The reaction proceeds via a radical mechanism and produces solid products, which can be isolated by filtration. The azole substrate only participates in the reaction when a functional group capable of accepting hydrogen is present on the adjacent carbon, suggesting that hydrogen bonding facilitates the stabilization of the diazoether transition state.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Junya Kitano, Yuji Nishii, Masahiro Miura
Summary: In this study, we report a novel synthesis method that achieves selective construction of C4-substituted benzofurans through a Rh-catalyzed reaction. This method avoids cumbersome multistep processes and has high synthetic efficiency.
Article
Chemistry, Organic
Cheng Li, Huawen Huang, Fuhong Xiao, Bin Zhao, Guo-Jun Deng
Summary: The study describes a practical strategy for skeletal diversification through combining selective C-H cleavage with C-C cleavage in a tandem reaction. Rhodium(iii)-catalyzed redox-neutral reaction of aryl oximes and internal alkynes generates novel N-(2-cyanoaryl) indanone imines with good yields, regioselectivities and atom economy, producing water as the only by-product. Experimental and theoretical studies offer mechanistic insights into this transformation, achieving an attractive integration of C-H activation with C-C activation in oxime transformation.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Jie Wang, Shan-Shan Wang, Jun Xiao, Yu-Jie He, Xin-Yan Wu, Xingguang Li, Pei-Nian Liu
Summary: CF3-substituted imidoyl sulfoxonium ylides (TFISYs) are versatile and powerful synthons for the synthesis of diverse CF3-substituted N-heterocycles, offering broad application prospects.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Satyajit Roy, Sandip Kumar Das, Hillol Khatua, Subrata Das, Krishna Nand Singh, Buddhadeb Chattopadhyay
Summary: An iron-catalyzed denitrogenative rearrangement of 1,2,3,4-tetrazole has been developed, showcasing the synthesis of complex-N-heterocyclic products and a short synthesis of a bioactive molecule. This discovery emphasizes the progress of radical activation strategy, which is expected to find wide application in medicinal chemistry, drug discovery, and natural product synthesis research.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Fuchao Yu, Daniel A. Valles, Weijie Chen, Scott D. Daniel, Ion Ghiviriga, Daniel Seidel
Summary: Secondary alicyclic amines are converted to alpha-aminonitriles by adding TMSCN to their corresponding imines, which are generated in situ via the oxidation of amine-derived lithium amides with simple ketone oxidants. Amines with an existing a-substituent undergo regioselective alpha'-cyanation, even if the C-H bonds at that site are less activated. Amine alpha-arylation can be combined with alpha'-cyanation to produce difunctionalized products in a single step.
Review
Chemistry, Organic
Jumreang Tummatorn, Somsak Ruchirawat, Charnsak Thongsornkleeb
Summary: Halogenative annulation of alkyne-tethered N- and O-containing arenes is a general strategy for constructing various halogenated N- and O-heterocycles. This method provides valuable synthetic building blocks carrying C(sp2)- halide functional groups, which are useful for cross-coupling reactions and other transformations. This Short Review examines different halogenative annulation methods for constructing aryl-fused halogenated N- and O-heterocycles, with a focus on recent technologies and the roles of halogenating agents.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Multidisciplinary
Song-Zhou Cai, Danhua Ge, Li-Wen Sun, Weidong Rao, Xin Wang, Zhi-Liang Shen, Xue-Qiang Chu
Summary: This study presents an efficient three-component tandem reaction of polyftuoroalkyl peroxides with sulfinates for constructing fluoroalkylated tetrasubstituted furan derivatives. The reaction proceeds via an unprecedented sequence, cleaving four C(sp(3))-F bonds and forming two new C-S bonds. It offers a transition metal-free C-F bond functionalization with broad substrate scope and excellent functional group tolerance.
Article
Chemistry, Organic
Juntao Yang, Bingxian Liu, Junbiao Chang
Summary: A ruthenium(II)-catalyzed one-pot synthesis of highly substituted 1,2-dihydropyridines (DHPs) via a three component reaction system has been successfully developed. The reaction utilizes a simple Ru(II) catalyst without the need for specific ligands. The catalytic system shows excellent functional group compatibility with a wide range of starting materials. The obtained DHPs can be easily converted into tetrahydropyridines and azabicyclo[4.2.0]octa-4,7-dienes by subsequent reduction or [2 + 2] cycloaddition reaction.
Article
Chemistry, Organic
Lin Li, Xin-Lian Liu, Jin-Yan Liang, Yong-Yu He, Ai-Jun Ma, Wei-Feng Wang, Jin-Bao Peng
Summary: A palladium-catalyzed dicarbonylation reaction of alpha-iodo-substituted ACPs has been developed for the synthesis of carbamoyl-substituted indenones. Two carbonyl groups are incorporated into the product by cleaving the proximal C-C bond of the ACPs. A broad range of carbamoyl-substituted indenones are efficiently prepared with good to excellent yields.
Article
Chemistry, Organic
Farrukh Sajjad, Yanmei Chen, Xue Tian, Suzhen Dong, Alavala Gopi Krishna Reddy, Wenhao Hu, Dong Xing
Summary: An efficient strategy for the construction of 1,4-oxazines from simple alpha-amino ketones and diazo pyruvates catalyzed by RuCl3 was reported, showing promising anticancer activities towards HCT116. This transformation involves a tandem N-H insertion/cyclization sequence via an enol formation under mild reaction conditions with broad functional group tolerance.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Song Zou, Zeyu Zhang, Chao Chen, Chanjuan Xi
Summary: The MeOTf-catalyzed intramolecular acyl-cyclization of aryl isocyanates provides (NH)-phenanthridinones and lactams under metal-free conditions, with good to excellent yields and tolerance for a variety of functional groups. The reaction can be scaled up to gram scale and used for the direct or short-step synthesis of natural alkaloids with high yields.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Yue Zhang, Jing Lu, Tianlei Lan, Shaoling Cheng, Wei Liu, Chao Chen
Summary: A new class of aliphatic amino iodane(III) reagents has been prepared, characterized by single-crystal X-ray diffraction. Additionally, a practical copper-catalyzed directed electrophilic amination of aryl amines using amino-iodane(III) as amination agents has been developed without the need for external additives.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(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
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, Organic
Shiyong Peng, Jieyin He, Liangliang Yang, Hong Zhang, Hongguang Li, Ming Lang, Chao Chen, Jian Wang
Summary: A phenyliodine(III) diacetate-promoted dearomative spirocyclization of phenolic ketones was controlled by 1,1,1,3,3,3-hexafluoroisopropanol to provide two libraries of structurally interesting compounds, spirocyclohexadienonic ketals and their acetoxylated counterparts, in moderate to excellent yields. Control experiments revealed that the reaction proceeds through a spirocyclohexadienone-oxocarbenium cation species.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Zhenyu Wang, Chengyao Kimmy Cao, Evgeny Tretyakov, Wei Liu, Chao Chen
Summary: The facile stereoselective bis-trifluoromethylselenolation reaction of alkyne derivatives was successfully achieved for the first time. By reacting alkyne derivatives with AgSeCF3 in the presence of N-bromosuccinimide and water, the desired bis-trifluoromethylselenolated products could be obtained in moderate-to-excellent yields. This new methodology allows for one-pot synthesis and has a wide substrate range.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(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
Chenxin Ge, Bin Wang, Yunchen Jiang, Chao Chen
Summary: In this study, the direct difluoroethylation reactions of N- and O-nucleophiles were achieved with a hypervalent iodine reagent DFVI via a neighbouring group rearrangement. The diverse reactivity of DFVI due to its unique electronic effect was explored and applied in the incorporation of difluoroethylene group.
COMMUNICATIONS CHEMISTRY
(2022)
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, 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)
