Article
Chemistry, Organic
Takahiro Soeta, Kota Kaneta, Yuichi Hatanaka, Tomonori Ida, Yutaka Ukaji
Summary: This paper discusses the N-heterocyclic carbene (NHC)-catalyzed redox monoacylation of 1,n-linear diols using alpha-benzoyloxyaldehydes, which resulted in moderate to good selectivities and chemical yields. The original NHC with a pyridine moiety played a crucial role in achieving good chemoselectivities, and a wide range of 1,n-linear diols were successfully applied in this reaction.
Article
Chemistry, Organic
Rurong Yu, Feiyue Hao, Xinyu Zhang, Zhongbing Fang, Zhengneng Jin, Guyue Liu, Guoliang Dai, Jiashou Wu
Summary: A method for selectively reducing 2-pyridyl ketones and related N-heteroaryl compounds using cobalt stearate as a catalyst and DMF as a hydride source has been developed. The chelation with cobalt activates the ketone substrate, making this method highly chemoselective. A possible reaction mechanism has been proposed based on control experiments.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Cheng-Yu Long, Hao Chen, Cheng Ma, Bo-Wei Zhao, Shen-Huan Li, Yue Cui, Xinge Yang, Shao-Fei Ni, Xue-Qiang Wang
Summary: A Ni-catalyzed protecting-group-free C-C coupling protocol has been developed for the efficient synthesis of 2,2'-biphenol derivatives. This newly developed strategy demonstrates remarkable chemoselectivity control ability, wide substrate scope, and excellent functional group tolerance.
Article
Chemistry, Organic
Jin Bai, Erdong Qu, Shangzhang Li, Riqian Zhu, Qinyue Deng, Wanfang Li
Summary: Here, we report a Ni-catalyzed cross-coupling reaction that produces ss-haloethyl esters with good yields and wide substrate scope. The presence of a cyclic triazene moiety in the benzotriazole is essential for the unique reactivity of these amides.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Sanxia Chen, Wenxuan Xue, Conghui Tang
Summary: An easily prepared core-shell heterogeneous nanocobalt catalyst was developed for the selective reduction of N-heteroarenes under mild conditions and ambient atmosphere. The catalyst showed high selectivity and efficiency in hydrogenating various derivatives. It also demonstrated good tolerance towards substrates with sensitive functional groups, and could be applied in liquid organic hydrogen storage system.
Article
Multidisciplinary Sciences
Xiao-Biao Yan, Lun Li, Wen-Qiang Wu, Lun Xu, Ke Li, Yu-Cheng Liu, Hang Shi
Summary: The authors demonstrate a method to add alkanes with an amino functionality to olefins using a nickel catalyst that utilizes the amine itself as the hydride source, eliminating the need for an external hydride reagent. This approach allows for the production of valuable, complex structural motifs and chiral alpha-branched amines in organic synthesis. Additionally, the use of a P-chiral ligand further enhances the catalytic efficiency of the reaction.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Bo Han, Hongmei Jiao, Rong Chen, Yuqi Zhang, Jijiang Wang
Summary: The first example of NHC (N-heterocyclic carbene) ligand-promoted reduction of imines and azobenzenes with a homogeneous silver catalyst is reported. The use of PhSiH3 induces hydrogenation of imines and azobenzenes, and the 1 mol% NHC-Ag precatalyst enables the retention of reducible functionalities and compatibility of sensitive groups, offering a mild and practical method for amine preparation with high turnover numbers (up to 9500). It has also been shown that the IPrAgCl/PhSiH3 combination is responsible for the selective C=O reduction of aldehyde and ketone analogues.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Masatoshi Shibuya, Takayuki Orihashi, Yamei Li, Yoshihiko Yamamoto
Summary: The chemoselective benzylic C(sp(3))-H amination of unprotected arylalkanols catalyzed by N-hydroxyphthalimide has been successfully developed, with the critical role played by 1,1,1,3,3,3-hexafluoropropan-2-ol as a solvent. The conversion of the aminated product to the corresponding free amino alcohol was also demonstrated in this study.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Applied
Dharmendra Kumar, Malleswara Rao Kuram
Summary: Easy access to divergent products through chemoselective copper-catalyzed carbene insertion onto N-H bonds of tryptamine derivatives is achieved by varying the nucleophilicity of the aliphatic NH and electron-donating or electron-withdrawing groups. The reaction provides N-H insertion products with broad substrate scope and good yields.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Zhongliang Cai, Junyi Zhou, Miao Yu, Liqin Jiang
Summary: The divergent chemoselective synthesis of 2-methylene-2,3-dihydrothiazoles and 4-benzylidene pyrrolidine-2-thiones (most with E stereoselectivity) from N-propargyl thiocarbamoyl fluorides and malonate esters has been accomplished, with one pathway providing 4-benzylidene pyrrolidine-2-thiones and another leading to 2-methylene-2,3-dihydrothiazoles through isomerization of alpha,alpha-diester thioamide intermediates.
Article
Chemistry, Multidisciplinary
Kathleen M. Morrison, Charles S. Yeung, Mark Stradiotto
Summary: A systematic evaluation of competitive bisphosphine/Ni-catalyzed C-N versus C-O cross-couplings involving model compounds enabled the development of selective O- and N-arylation of amino alcohols with (hetero)aryl chloride electrophiles, without the need for protection group chemistry. The use of the CyPAd-DalPhos pre-catalyst C2 allowed for challenging O-arylation in amino alcohols with branched alkylamine groups, while selective N-arylation was observed in substrates with less hindered linear alkylamine and aniline groups. The reaction scope in (hetero)aryl chloride was broad, and the transformations could be conducted using benchtop handling of materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yusaku Yoshiwara, Shunsuke Kotani, Makoto Nakajima
Summary: The asymmetric catalytic transformations of N-unprotected cyclic carboxyimides provide a direct route to access a variety of biologically valuable chiral compounds, such as succinimides, hydantoins, oxazolidinediones, and glitazones. The reaction involves the formation of a bis(trichlorosilyl) nucleophilic intermediate from cyclic carboxyimides, which then reacts with aldehydes through a cyclic transition state, leading to highly enantioselective aldol reactions. Additionally, N-unprotected carboxyimides can be chemoselectively activated, even in the presence of N-alkylated carboxyimides, for stereoselective and chemoselective aldol reactions via in situ silicon tetrachloride activation. The functionalized cyclic carboxyimides can be easily derivatized to various chiral building blocks without the need for unnecessary protection/deprotection steps.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Tian You, Junqi Li
Summary: In this study, a C-N cross-coupling reaction using Ni(cod)(DQ) as a catalyst without additional ligands was reported. This method enables the synthesis of N,N-diarylsulfonamides from weakly nucleophilic N-arylsulfonamides and aryl bromides. The reaction is compatible with a wide range of electron-deficient and electron-rich aryl and heteroaryl bromides and can be applied to the derivatization of N-arylsulfonamide pharmaceutical compounds.
Article
Chemistry, Multidisciplinary
Liye Chen, Katerina G. Malollari, Adam Uliana, John F. Hartwig
Summary: The lack of functional groups in polyolefins limits their applications, but the functionalization of C-H bonds holds promise for incorporating functionalities into ethylene and linear alpha-olefins polymers. The selective functionalization of polyolefins derived from branched alkenes has not been achieved due to steric effects, but a polyfluorinated ruthenium-porphyrin catalyst successfully incorporates ketone units into polyisobutene without chain cleavage, resulting in a thermally stable polymer with enhanced wetting properties.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Xiaofeng Liu, Ying Shao, Jiangtao Sun
Summary: A ruthenium-catalyzed highly chemoselective N-alkylation of 2-pyridones has been developed, providing N-alkylated 2-pyridone derivatives in good yields and excellent N-selectivity. The key to this unprecedented reaction is the use of CpRu(PPh3)(2)Cl as the catalyst and sulfoxonium ylides as the alkylation reagents, which can also be applied to 7-azaindoles with slight variations in reaction conditions. Furthermore, sulfonium ylides are also suitable alkylation reagents for good selectivity in N-alkylation of 2-pyridones.
Article
Chemistry, Multidisciplinary
Xiu-Ning Hu, Dong-Ping Wu, Ye-Peng Xu, Pei-Qiang Huang
Summary: The first organocatalytic asymmetric synthesis of an advanced intermediate of (+)-sarain A was achieved by combining organocatalytic asymmetric Michael addition reaction and a nitrogen-to-carbon chirality transfer. This method allows for the construction of three chiral centers and chemoselective reduction of a key lactam intermediate, providing a tricyclic intermediate with all necessary functionalities for further elaboration into (+)-sarain A.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Dong-Huang Chen, Wei-Ting Sun, Cheng-Jie Zhu, Guang-Sheng Lu, Dong-Ping Wu, Ai-E Wang, Pei-Qiang Huang
Summary: The combination of transition-metal catalysis and organocatalysis has enabled chemists to achieve direct enantioselective reductive cyanation and phosphonylation of secondary amides, synthesizing enantioenriched chiral alpha-aminonitriles and alpha-aminophosphonates for the first time. The protocol is efficient, enantioselective, scalable, and the thiourea catalyst can be recycled and reused.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Su-Yu Huang, Long-Hui Gao, Xiong-Zhi Huang, Pei-Qiang Huang
Summary: This article provides a detailed account of the synthetic efforts towards the enantioselective total synthesis of the complex alkaloid methoxystemofoline. The key steps include Keck allylation, olefin cross-metathesis, regioselective aldol addition, and Overman's method for moiety installation. The final step resulted in the formation of both the proposed structure of methoxystemofoline and its E-stereoisomer in a 1:1 ratio, leading to the suggestion to rename the natural product as isomethoxystemofoline.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Heng-Hui Li, Jia-Qi Li, Xiao Zheng, Pei-Qiang Huang
Summary: A decarboxylative cross-coupling reaction of alpha-amino acids with nitrones via visible-light-induced photoredox catalysis has been established, providing easy access to beta-amino hydroxylamines and vicinal diamines with structural diversity. This protocol offers efficient synthetic strategies for some valuable molecules containing vicinal diamine groups.
Article
Chemistry, Organic
Yi Lin, Shu-Fan He, Hui Geng, Yu-Chen Xiao, Kan-Lei Ji, Jian-Feng Zheng, Pei-Qiang Huang
Summary: A facile method for the preparation of 2,3-dialkylsubstituted quinazolinones from readily available N-arylamides and commercial isocyanates was developed, which involves the activation of the secondary amide with Tf2O/2-Br-Pyr, sequential addition of isocyanate, and cyclization. The mild reaction is general for a wide range of substrates and can be run on a gram scale.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Qian He, Jian-Liang Ye, Fang-Fang Xu, Hui Geng, Ting-Ting Chen, Hang Chen, Pei-Qiang Huang
Summary: The research findings demonstrated that Tf2O/TTBP can be an alternative amide activation system for the direct transformation of both secondary and tertiary amides, generally obtaining higher or comparable yields. Additionally, the combination of Tf2O/TTBP was also effective in promoting various important reactions, leading to concise and high-yield syntheses of natural products.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Si-Jia Yu, Jian-Liang Ye, Ya-Cheng Hong, Pei-Qiang Huang
Summary: This paper describes the construction of functionalized and fused eight-membered carbocycles by triflic anhydride-mediated cyclization of 7-enamides. The reactions proceed smoothly to afford nonconjugated beta,gamma-enimines, conjugated alpha,beta-enimines, or fused 5/8 ring systems in good yields. Acidic hydrolysis of the cyclization reactions leads directly to the corresponding alpha,beta-enones, providing an efficient access to pendent cyclic beta,gamma-enimines/enones for some substrates.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Ying-Hong Huang, Zhan-Jiang Liu, Pei-Qiang Huang
Summary: This study describes the successful total synthesis of (+)-cylindricine D and its epi-isomer, as well as the synthesis of (+)-cylindricine C and E using a highly efficient method.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Dong-Ping Wu, Wei Ou, Pei-Qiang Huang
Summary: This study describes the catalytic reductive condensation reactions between tertiary amides and active methylene compounds, leading to multifunctionalized non-N-containing products. The reactions proceed through a sequential process involving iridium-catalyzed hydrosilylation of the amides followed by acid-mediated condensation with the active methylene compounds. This scalable method demonstrates a broad scope and remarkable chemoselectivity for the amide group in the presence of various sensitive or even more reactive functionalities such as ester, cyano, nitro, silyl dienol ether, and ketone.
Article
Multidisciplinary Sciences
Hang Chen, Zhi-Zhong Wu, Dong-Yang Shao, Pei-Qiang Huang
Summary: The catalytic asymmetric geminal bis-nucleophilic addition to nonreactive functional groups is a highly desirable yet challenging transformation in organic chemistry. In this study, the first catalytic asymmetric reductive/deoxygenative alkynylation of secondary amides was reported. The method combines iridium/copper relay catalysis with organocatalysis and allows the efficient synthesis of a variety of chiral a-branched amines. The protocol also demonstrates excellent enantioselectivity, chemoselectivity, and functional group tolerance.
Article
Chemistry, Multidisciplinary
Kan-Lei Ji, Shu-Fan He, Dong-Dong Xu, Wen-Xin He, Jian-Feng Zheng, Pei-Qiang Huang
Summary: A concise asymmetric total synthesis of (-)-quinocarcin has been achieved through high step economy using commercially available starting materials. The key chiral pyrrolidine intermediate with three stereocenters was prepared via a catalytic enantioselective reductive 1,3-dipolar cycloaddition reaction. This synthesis also involved a Rh-III-catalyzed C-H activation/cyclization and a tandem diastereoselective hydrogenation/cyclization to construct the tetrahydroisoquinoline-pyrrolidine tetracyclic core unit of quinocarcin.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Multidisciplinary Sciences
Fang-Fang Xu, Jin-Quan Chen, Dong-Yang Shao, Pei-Qiang Huang
Summary: The study presents a unified strategy for the synthesis of various alkaloids using readily available amides and alkynes, which is important for drug and agrochemical discovery.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Hang Chen, Dong-Huang Chen, Pei-Qiang Huang
Summary: This study demonstrates the catalytic intermolecular decarbamoylative C-C arylation and C-B borylation of N-acylpyrrole-based tertiary amides using nickel,N-heterocyclic carbene (NHC) catalysis. The research is significant for the direct transformation of amides.
CELL REPORTS PHYSICAL SCIENCE
(2023)
Article
Chemistry, Organic
Si-Jia Yu, Jie Li, Jian-Liang Ye, Pei-Qiang Huang
Summary: A one-pot reaction using palladium catalyst has been developed for the synthesis of bicyclic 1,3-oxazin-4-ones, 2,3,6,7-tetrahydrocyclopenta[e]-1,3-oxazin-4-ones and 2,3,5,6,7,8-hexahydro-4H-benzo[e]-1,3-oxazin-4-ones. The reaction shows good yields, broad substrate scope, mild reaction conditions, and scalability. It also demonstrates good compatibility with acetyl chloride and phenylacetyl chloride for the synthesis of monocyclic 1,3-oxazin-4-ones.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Hui-Rong Lu, Hui Geng, Guan-Tian Ding, Pei-Qiang Huang
Summary: We report a catalyst- and solvent-free method to synthesize enantioenriched secondary amides. The method is simple, mild, versatile, and efficient with high selectivity, and can be applied to different types of asymmetric products and alpha-branched primary amines.
Article
Chemistry, Multidisciplinary
Xuemei Liu, Chaonan Cui, Shuoshuo Wei, Jinyu Han, Xinli Zhu, Qingfeng Ge, Hua Wang
Summary: This study presents a new strategy for designing efficient photocatalysts that can convert CO2 into hydrocarbons by utilizing synergistic catalytic sites. The findings provide a solution for the selective photocatalytic reduction of CO2 to CH4.
Article
Chemistry, Multidisciplinary
Chengxian Hu, Dan Wang, Lu Wang, Ying Fu, Zhengyin Du
Summary: A novel one-pot, three-component reaction conducted under electrochemical conditions was studied. The reaction involved 2-aminothiophenols, aldehydes, and malononitrile, using TBABF4 as an electrolyte and CuI as a catalyst. The proposed reaction mechanism suggested that CuI served as an electron relay. This method offers simplified operation, high atom economy, and mild reaction conditions.
Article
Chemistry, Multidisciplinary
Zhi Yang, Yu Chen, Linxi Wan, Yuxiao Li, Dan Chen, Jianlin Tao, Pei Tang, Fen-Er Chen
Summary: A highly enantioselective method for the complete hydrogenation of pyrimidinium salts using Ir/(S,S)-f-Binaphane complex as the catalyst was developed. This method provides easy access to fully saturated chiral hexahydropyrimidines, which are prevalent in many bioactive molecules. The reactions exhibit high yields and enantioselectivities under mild reaction conditions without additives. Successful application of this methodology in a continuous flow fashion further extends its practical utility.
Article
Chemistry, Multidisciplinary
Tina Jeoh, Jennifer Danger Nill, Wujun Zhao, Sankar Raju Narayanasamy, Liang Chen, Hoi-Ying N. Holman
Summary: In this study, the enzymatic hydrolysis of cellulose was investigated using real-time infrared spectromicroscopy. The spatial heterogeneity of cellulose was found to impact the hydrolysis kinetics. Hydration affected cellulose ordering, and Cel7A preferentially removed less extensively hydrogen bonded cellulose.
Article
Chemistry, Multidisciplinary
Tiphaine Richard, Walid Abdallah, Xavier Trivelli, Mathieu Sauthier, Clement Dumont
Summary: An effective method of grafting functionalities onto lignin based on glycerol carbonate has been developed using an efficient nickel-catalysed telomerisation reaction. This method allows lignin to have new reactive functions and reduces the glass transition temperatures of modified lignins, thereby expanding the application range of lignin-based resins.
Article
Chemistry, Multidisciplinary
Jing Qi, Xiyan Wang, Gan Wang, Srinivas Reddy Dubbaka, Patrick ONeill, Hwee Ting Ang, Jie Wu
Summary: This study presents a green and environmentally friendly approach for the synthesis of imides using electrocatalytic oxidation with H2O as the oxygen source. The method eliminates the need for toxic or expensive oxidants and achieves high yields under mild reaction conditions. It shows broad substrate compatibility and potential for industrial applications.
Article
Chemistry, Multidisciplinary
Babasaheb Sopan Gore, Lin-Wei Pan, Jun-Hao Lin, Yi-Chi Luo, Jeh-Jeng Wang
Summary: Here, we report a visible light-promoted intramolecular radical cascade reaction for the construction of fluorenol and naphthalene-fused cyclopropyl carbaldehyde derivatives. This method offers mild reaction conditions, a broad substrate scope, excellent step efficiency, and scalability, without the need for external chemical oxidants. The novelty of this protocol was demonstrated by synthesizing chrysene analogs and performing late-stage functionalizations.
Article
Chemistry, Multidisciplinary
Juho Antti Sirvio, Idamaria Romakkaniemi, Juha Ahola, Svitlana Filonenko, Juha P. Heiskanen, Ari Ammala
Summary: This article discusses the method of using supramolecular interaction between an aromatic hydrogen bond donor and lignin to achieve rapid delignification of softwood at low temperatures.
Article
Chemistry, Multidisciplinary
Yunyan Meng, Chunxiang Pan, Na Liu, Hongjiang Li, Zixiu Liu, Yao Deng, Zixiang Wei, Jianbin Xu, Baomin Fan
Summary: A novel visible light-driven synthesis method for 2,3-diamines has been developed, which has mild conditions, avoids the use of metal reagents, and can synthesize diamines and diols in one pot.
Article
Chemistry, Multidisciplinary
Mingqing Huang, Haiyang Huang, Mengyao You, Xinxin Zhang, Longgen Sun, Chao Chen, Zhichao Mei, Ruchun Yang, Qiang Xiao
Summary: A direct air-oxidized strategy for the synthesis of benzo[b]phosphole oxides was developed in this study. Arylphosphine oxides were transformed into phosphinoyl radicals, which were further combined with various alkynes to achieve the desired products. DFT calculations revealed the mechanism of phosphinoyl radical formation.
Article
Chemistry, Multidisciplinary
Anwei Wang, Jiayin Huang, Chunsheng Zhao, Yu Fan, Junfeng Qian, Qun Chen, Mingyang He, Weiyou Zhou
Summary: This study demonstrates an innovative strategy for the aerobic oxidation of C(sp(3))-H bonds using gamma-valerolactone. By optimizing the reaction conditions and utilizing specific catalysts, efficient oxidation of C(sp(3))-H bonds is achieved with good chemoselectivity in certain cases.
Article
Chemistry, Multidisciplinary
Shun Li, Likai Tong, Zhijian Peng, Bo Zhang, Xiuli Fu
Summary: Sulfide compounds show promise as electrocatalysts for water splitting, but their performance is limited by factors such as limited active sites and hindered substance transport. This study successfully prepared a high-entropy sulfide (ZnCoMnFeAlMg)(9)S-8, which reduced grain size and increased specific surface area, enabling the realization of a dual-functional catalyst with multiple catalytic sites. High entropy also modulated the electronic properties of sulfides, reducing the potential energy barrier for hydrolysis. This research introduces a new approach for functionalizing high entropy nanomaterials and improves the performance of water splitting catalysts.
