Article
Chemistry, Organic
Chunlan Zhou, Haolin Zheng, Ya Chen, Guojiang Mao, Guo-Jun Deng
Summary: A metal-free four-component synthesis of tetrasubstituted pyrroles was developed using ammonium salt as the nitrogen source. This strategy involves [2 + 1 + 1 + 1] condensation to form the pyrrole ring in one pot. By utilizing 1,4-naphthoquinones and maleimides as versatile C2 fragments, substituted benzo[f]isoindole-4,9-diones and pyrrolo[3,4-c]pyrrole-1,3-diones were obtained. This work is notable for its use of ammonium salt as the nitrogen source, readily available starting materials, and multibond formation within a single operation.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Michael P. Doyle, Ming Bao
Summary: This study achieved a highly enantioselective synthesis of substituted pyrrolidines and 1,2-oxazinanes via stereoretentive [3 + 2]/[3 + 3]-cycloaddition of nonracemic donor-acceptor cyclopropanes with imines, triazines, and nitrones. The reactions were conducted under mild conditions and showed good to high yields with broad applicability. Compared to previous approaches using racemic cyclopropane reactants and chiral ligand catalysts, this study utilized enantioenriched donor-acceptor cyclopropanes as reactants with achiral catalysts.
Article
Chemistry, Organic
Bubul Das, Nikita Chakraborty, Kamal Krishna Rajbongshi, Bhisma K. Patel
Summary: This article reviews different methods and approaches for the synthesis of N/O/S-heterocycles using styrene as an annulating partner in the past five years. These heterocycles are widely present in the core structure of various natural products, pharmaceuticals, and agrochemicals.
Article
Chemistry, Multidisciplinary
Johanna Proessdorf, Christian Jandl, Thomas Pickl, Thorsten Bach
Summary: It was found that while 2-alk-omega-enyloxy-sustituted benzaldehydes do not display any photochemical reactivity at the arene core, the respective iminium perchlorates undergo efficient reactions under certain conditions, leading to products with different molecular structures and stereochemical features.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Bedadyuti Vedvyas Pati, Asit Ghosh, Komal Yadav, Shyam Kumar Banjare, Shalini Pandey, Upakarasamy Lourderaj, Ponneri C. Ravikumar
Summary: The stereoselective synthesis of 1,3-enynes from 1,3-diynes was achieved by palladium-catalyzed selective C-C bond cleavage of cyclopropanol. The protocol showed high stereoselectivity with diverse substrates. Mechanistic investigations and DFT calculations were carried out to validate the atomic-level mechanism and identify rate-controlling states in the catalytic cycle. Preliminary investigations ruled out the involvement of the radical pathway in this transformation.
Article
Chemistry, Organic
Xiao-Xia Ming, Shuai Wu, Ze-Yu Tian, Jia-Wei Song, Cheng-Pan Zhang
Summary: The study confirmed the potential of (2-bromoethyl)diphenylsulfonium triflate as a powerful vinylation reagent in Sonogashira cross-coupling reactions. The vinylation proceeded smoothly at 25 degrees C under Pd/Cu catalysis, yielding a variety of 1- and 2-unsubstituted 1,3-enynes in moderate to excellent yields. This protocol represents the first application of (2-haloethyl)diphenylsulfonium triflate as a CH=CH2 transfer source in organic synthesis.
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
Chemistry, Multidisciplinary
Min Gao, Yanshu Luo, Qianlan Xu, Yukun Zhao, Xiangnan Gong, Yuanzhi Xia, Lin Hu
Summary: The research achieved a unified catalytic asymmetric (N+1) (N=4, 5) annulation reaction of oxindoles with bifunctional peroxides using a chiral phase-transfer catalyst (PTC). This method provides a distinct way to access valuable chiral spirooxindole-tetrahydrofurans and -tetrahydropyrans with good yields and high enantioselectivities under mild conditions. The DFT calculations were performed to rationalize the high enantioselectivity observed in the reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Yu-Ting Tian, Fa-Guang Zhang, Jun-An Ma
Summary: A regioselective [3 + 2] cyclo-addition reaction of 3-alkynoates with Seyferth-Gilbert reagent was developed with the trigger of Et3N to produce a series of trisubstituted pyrazole-3-phosphonates. A one-pot cycloaddition/alkylation sequence was further utilized to access the fully substituted pyrazoles.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
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, Organic
Nai-Chen Hsueh, Yu-Han Wang, Meng-Yang Chang
Summary: We describe an efficient tBuOK-mediated sequential condensation and double desulfonylative cyclopropanation of readily accessible 1,2-bis(sulfonylmethyl)arenes with 3-arylacroleins. This single-step strategy provides a variety of polysubstituted biscyclopropane-fused tetralins with six contiguous stereogenic centers via the construction of five carbon-carbon single bonds. A plausible mechanism is proposed and discussed. Water and sulfinic acid salts are generated as the byproducts in the overall reaction process.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Hai-Jun Leng, Qing-Zhu Li, Peng Xiang, Ting Qi, Qing-Song Dai, Zhi-Qiang Jia, Chuan Gou, Xiang Zhang, Jun-Long Li
Summary: A novel oxindole-based azaoxyallyl cation synthons were designed for [3+1] cyclization with sulfur ylides, leading to facile production of 3,3-spiro[beta-lactam]-oxindoles with up to 94% yield and perfect diastereoselectivity.
Article
Chemistry, Multidisciplinary
Bang-Yi Wei, Dong-Tai Xie, Sheng-Qiang Lai, Yu Jiang, Hong Fu, Dian Wei, Bing Han
Summary: This study demonstrates the first [4+2] annulation of hydroxamic acids with olefins to synthesize benzo[c][1,2]oxazines scaffold under mild conditions with high selectivity, and shows how the product selectivity can be tuned by changing the anode material.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Baihui Zheng, Xiaotong Li, Yang Song, Shuyang Meng, Yifei Li, Qun Liu, Ling Pan
Summary: A visible-light-induced [3+2] oxidative cyclization of alkynes with ketene dithioacetals in the presence of an acridine photosensitizer was reported, leading to regioselective synthesis of multisubstituted thiophenes in high yields under metal-free conditions. This reaction showed good substrate tolerance and efficiency in large-scale syntheses. The reaction mechanism and applications were detailed to illustrate the reactivity of the new 1,3-dipoles and the selectivity of the reactions.
Article
Chemistry, Organic
Xiaoxiang Zhang, Yingying Zhang, Xiaoting Gu, Zhuan Zhang, Wanxing Wei, Taoyuan Liang
Summary: A copper-mediated 2,3-difunctionalization of indoles to afford 3-halogenated 2,3 '-biindoles is described. The protocol uses readily available feedstocks and a naturally abundant copper catalyst system, which allows the regioselective formation of C-C and C-X (X = Cl & Br) bonds in one single operation. Copper metal salt serves not only as a catalyst but also as a reactant to provide the source of halogen, avoiding the use of environmentally unfriendly reagents and displaying good functional group compatibility.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Yangyang Ma, Leiyang Lv, Zhiping Li
Summary: An efficient and selective synthesis method for perfluoroalkyl-group-substituted benzo[4,5]imidazo[1,2-a]-pyridines has been developed. It utilizes beta-perfluoroalkyl peroxides as novel fluorinated C3-building blocks for regioselective [3 + 3] annulation with 2-cyanomethyl benzimidazole under metal-free conditions. The application of the synthesized perfluoroalkylated BIPs as potent anticancer reagents demonstrates the biological utility of this method.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Leilei Wang, Leiyang Lv, Zhiping Li
Summary: In this study, the concomitant functionalization of two distinct alpha-C-H bonds of carbonyls integrated with unactivated olefins and tert-butyl hydroperoxide was achieved in one pot using Bronsted acid catalysis and radical relay coupling. The method yielded a variety of structurally valuable unsymmetrical peroxy 1,9-diketones in moderate to good yields under metal-free conditions.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Applied
Ge Gao, Kuantao, Mao, Leiyang Lv, Zhiping Li
Summary: A metal-free three-component coupling of alpha-CF3 carbonyls, azides and amines has been developed for the regioselective synthesis of 1,4,5-trisubstituted 1,2,3-triazoles in air. The reaction conditions and substrate structures can be controlled to obtain different products.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Physical
Leiyang Lv, Huijun Qian, Anna B. Crowell, Shuming Chen, Zhiping Li
Summary: This study reports a catalytic method for controlling the selectivity of reactions, allowing access to diverse fluorinated 1,5-dienes from the same starting materials. Density functional theory calculations also revealed a ligand design for switching selectivity. This ligand-controlled approach is important for late-stage modification of complex molecules.
Article
Multidisciplinary Sciences
Jian Kan, Zhangpei Chen, Zihang Qiu, Leiyang Lv, Chenchen Li, Chao-Jun Li
Summary: This study reports a direct deoxygenative allylation and olefination of carbohydrates by using an umpolung strategy of carbohydrate carbonyls. This method overcomes the intrinsic problems of carbohydrates, allowing selective functionalization of natural carbohydrates.
Review
Chemistry, Physical
Leiyang Lv, Huijun Qian, Zhiping Li
Summary: This review summarizes the advances in catalytic ring-opening reactions of gem-Difluorocyclopropanes (F(2)CPs) under transition-metal catalysis, with a particular emphasis on the reactivities and applications of non-activated compounds.
Article
Chemistry, Organic
Leilei Wang, Shiming Shu, Leiyang Lv, Zhiping Li
Summary: The trifluoromethylthiolation-peroxidation of unactivated alkenes using readily-available AgSCF3 and tertbutyl hydroperoxide in the presence of a copper catalyst has been achieved. The reaction involves the radical trifluoromethylthiolation of alkenes and subsequent 1,5-HAT and remote alpha-CAH bond peroxidation, leading to the formation of a series of distal trifluoromethylthiolated organic peroxides with moderate to good yields and excellent regioselectivity under mild conditions.
TETRAHEDRON LETTERS
(2022)
Article
Chemistry, Organic
Kuantao Mao, Yangyang Ma, Leiyang Lv, Zhiping Li
Summary: A facile protocol for the synthesis of 1,3,4-oxadiazoles has been developed using [4+1] cyclization of alpha-CF3 carbonyls and hydrazides. This method utilizes readily available starting materials and offers simple and mild reaction conditions. Furthermore, synthetic transformation of the 1,3,4-oxadiazole product has also been investigated.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Yani Luo, Leiyang Lv, Zhiping Li
Summary: This study disclosed an efficient copper-catalyzed reaction for alkenes, germanium hydrides, and trimethylsilyl azide, allowing the introduction of germyl and azide groups across double bonds in a highly selective manner. The resulting compounds have significant value and can be further converted into commonly used compounds in organic synthesis.
Article
Chemistry, Multidisciplinary
Huijun Qian, Hieu D. Nguyen, Leiyang Lv, Shuming Chen, Zhiping Li
Summary: The study developed an efficient method to incorporate the hydrazone moiety into the products through palladium/NHC-catalyzed fluoroallylation/annulation of gem-difluorocyclopropanes (gem-F(2)CPs) with hydrazones. Thermodynamically unstable fluorinated E-allylation products were obtained with aryl ketone hydrazones, while monofluorinated products with branched selectivity were obtained with di-alkyl ketone hydrazones. Two kinds of pyrazoles were obtained via a defluorinative allylation/annulation cascade with aldehyde hydrazones, and different carbon atoms of gem-F(2)CPs could be incorporated into the pyrazole rings regiospecifically. DFT calculations revealed that the divergent selectivity was kinetically controlled and the final C-C bond formation proceeded through a 7-membered TS.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Yani Luo, Leiyang Lv, Zhiping Li
Summary: The light-promoted regioselective germylation of aryl propiolamides/alkynoates with germanium hydrides is described. Spiro[4.5]trienones containing germanium were obtained using N-arylpropiolamides via sequential C-Ge and C-C bond formation, while aryl alkynoates delivered vinylgermanes through radical Smiles rearrangement and CO2 release.
Article
Chemistry, Organic
Yuxuan Yan, Huijun Qian, Leiyang Lv, Zhiping Li
Summary: In this study, a Pd-IHept (NHC = N-heterocyclic carbene) catalyzed defluorinative functionalization approach was reported for the synthesis of monofluoroalkenes from gem-difluorocyclopropanes and malonates. The flexible yet sterically hindered N,N'-bis(2,6-di(4-heptyl)phenyl)imidazol-2-ylidene ligand played a key role in ensuring high reaction efficiency. Additionally, sterically hindered 1,1- and 1,2-disubstituted gem-difluorocyclopropanes could also be used in this transformation.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Kuantao Mao, Leiyang Lv, Zhiping Li
Summary: An efficient and selective transformation of 2,2,2-trifluoroethylcarbonyls into ureas/amides with amines has been reported. This reaction allows the selective cleavage of the C-C bond of 2,2,2-trifluoroethylcarbonyls under transition metal-free and oxidant-free conditions, which is different from the functionalization of the analogous C-F or C-CF3 bond. The reaction demonstrates the unexplored reactivity of 2,2,2-trifluoroethyl carbonyls and shows a broad substrate range and good functional group tolerance.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Chenhao Lou, Yuting Feng, Qiuwei Huang, Leiyang Lv, Zhiping Li
Summary: A visible light-induced decarboxylative peroxidation of carboxylic acids has been disclosed. With this protocol, a variety of readily available carboxylic acids were converted to the stabilized organic peroxides in moderate to good yields via decarboxylative radical C-OO bond coupling. Tert-butyl hydroperoxide acts as both the oxidant and peroxyl source, avoiding the use of transition metals or extra oxidants.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Leiyang Lv, Huijun Qian
Summary: This article summarizes the developments and advancements of allyl-(aza)allyl coupling reactions in recent years. Pd-catalyzed allyl-allyl couplings did not attract much attention from chemists for almost 20 years since the first report in 1980. Transition-metal-catalyzed allyl-(aza)allyl transformations have gained vital interest and significant development in many aspects over the last two decades, including metal-catalyst, ligand development, mechanistic understanding, substrate scope, and applications in preparing complex functional molecules. The review is organized based on the transition metals used in allyl-allyl coupling reactions, including the authors' own work. Additionally, transition-metal-free allyl-azaallyl cross-couplings and their applications in total synthesis of natural products and drugs are also included.
GREEN SYNTHESIS AND CATALYSIS
(2023)
