Article
Chemistry, Organic
Mei Wang, Yong-Qin He, Yao Zhu, Zhi-Bin Song, Xiao-Yu Wang, Hai-Yang Huang, Ban-Peng Cao, Wan-Fa Tian, Qiang Xiao
Summary: The study reports a wavelength-regulated, methylene blue organic dye-catalyzed method for the stereodivergent synthesis of (Z)- and (E)-1,4-enediones from stabilized phosphorous ylides. The method shows broad substrate and functional group tolerance. Mechanistic studies suggest singlet-oxygen-promoted (E)-alkene formation via a possible phospha-1,2-dioxetane intermediate, followed by a blue-LED triggered (E) -> (Z) isomerization reaction.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Akashdeep Sharma, Paru Jamwal, Ramani Gurubrahamam
Summary: This study presents a highly efficient and stereoselective route for the synthesis of 1,4-dicarbonyl 2,3-dihaloalkenes. By using stable unprotected alkynyl hydrazones and commercially available N-halosuccinimides, gamma-oxo-alpha, beta-(Z)-dihaloenoates were successfully obtained with high yields and complete Z-selectivity. The protocol also allows for the synthesis of vicinal dihaloalkenes with two different halogen atoms. In addition, a straightforward one-pot synthesis of dihaloenoates from readily accessible compounds was demonstrated, and potential applications of 4-oxo-2,3-dibromoenoates were explored, including the synthesis of valuable five- and six-membered heterocycles.
Article
Chemistry, Multidisciplinary
Yinsong Zhao, Shaozhong Ge
Summary: A chromium-catalyzed reaction has been developed for the synthesis of boryl-functionalized skipped dienes. By utilizing a dimerization/hydroboration process, the target product can be obtained efficiently and with good selectivity. EPR spectroscopic studies suggest that the reaction proceeds through a chromium(I) hydride intermediate.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Majeed Irfan, Rong Deng, Idrees Sumra, Xiao-Feng Zhu, Tingting Liu, Zhuo Zeng
Summary: A straightforward strategy was developed to utilize the impact of configuration on fluorescence and anti-cancer activity, resulting in the synthesis of E, E isomers with higher fluorescence efficiency and longer lifetime, and E, Z isomers with remarkable anticancer activity against human nasopharyngeal carcinoma.
Article
Chemistry, Organic
Chengniu Wang, Jin Dong, Tingting Li, Xi Zhao, Dawei Xu
Summary: A palladium-catalyzed semihydrogenation of alkynes to E- and Z-alkenes using EtOH as the hydrogenating agent is reported. The selectivity of the reaction can be effectively controlled by the choice of ligand/additive and solvent. The use of specific ligand/additive and solvent in the reaction enables stereoselective semihydrogenation of alkynes, and the method demonstrates broad applicability in the synthesis of various alkenes.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Organic
Peter Kisszekelyi, Tibor Penaska, Klara Stankovianska, Maria Meciarova, Radovan Sebesta
Summary: In this study, the synthesis and utilization of derivatives of 4H-benzo[b][1,4]thiazine-3-carboxylic acid were presented. These benzothiazine compounds were synthesized through the coupling reaction of aminothiols and bromopyruvates, and the oxidative dimerization of the starting materials was observed. Furthermore, the coupling of benzothiazines with amino acids enabled the enantioselective synthesis of the nonproteinogenic amino acid 2-amino-3-propylhexanoic acid.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Fengjie Huang, Zhidao Huang, Guixia Liu, Zheng Huang
Summary: A trans-semihydrogenation of 1,3-enynes with ethanol was developed using a new (PCN)Ir complex and tBuNH2 as catalysts, providing an efficient synthesis of unsymmetrical (E,E)-1,4-diarylbutadienes.
Article
Chemistry, Organic
Shashank Tripathi, Monty Kumar, Mayur D. Ambule, Ankit Saxena, Ruchir Kant, Sanjeev K. Shukla, Ajay Kumar Srivastava
Summary: Stereoselective difunctionalizations of alkynes were achieved to prepare (Z)-/(E)-fi-sulfonylacrylamides. The (Z)-fi-sulfonylacrylamides were generated via a one-pot process, while the (E)-fi-sulfonylacrylamides were prepared in a two-step synthesis.
Article
Chemistry, Multidisciplinary
Runze Mao, Daniel J. J. Wackelin, Cooper S. S. Jamieson, Torben Rogge, Shilong Gao, Anuvab Das, Doris Mia Taylor, K. N. Houk, Frances H. H. Arnold
Summary: By engineering bacterial cytochrome P450, chiral 1,2,3-polysubstituted cyclopropanes can be synthesized regardless of the stereopurity of the olefin substrates used. This new method simplifies the synthesis of chiral cyclopropanes and expands the application of classical cyclopropanation methods.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Tiantian Chen, Yashi Zou, Yanhua Hu, Zhenfeng Zhang, Hao Wei, Liangming Wei, Wanbin Zhang
Summary: An efficient asymmetric hydrogenation of internal simple enamides has been achieved using the diphosphine-cobalt-zinc catalytic system. The Ph-BPE ligand can achieve convergent asymmetric hydrogenation of E/Z-substrates. High yields and excellent enantioselectivities were obtained for different types of enamides. The hydrogenated products can be used for the synthesis of useful chiral drugs. Reasonable catalytic mechanism and stereocontrol mode are proposed based on DFT calculations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Zheye Zhang, Jiaining Liu, Shang Gao, Bo Su, Ming Chen
Summary: We describe the stereoselective syntheses of (E)- and (Z)-crotylboronates with alpha,alpha-disubstitution. The alkylation reaction exclusively occurs at the alpha position to the boryl groups in the starting crotylboronates, resulting in the desired boronates while maintaining the original alkene geometries. The resulting alpha,alpha-disubstituted crotylboronates can undergo aldehyde addition to afford allylated products with high stereoselectivities.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Tao Ye, Fangyuan Cheng, Jian Zhang, Yang-Zi Liu, Quannan Wang, Wei-Ping Deng
Summary: In this paper, a palladium-catalyzed C-H carbonylation reaction of gem-disubstituted ethylenes with phenyl formate as a convenient CO surrogate is reported. The reaction proceeds through an aryl to vinyl 1,4-palladium migration, providing a wide range of beta, beta-diaryl substituted alpha, beta-unsaturated esters with high efficiency and excellent regio- and stereoselectivities. The synthetic protocol presented in this study offers a convenient and powerful method to directly access a key intermediate for (Z)-tamoxifen.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Jiaming Liu, Shang Gao, Evangelos Miliordos, Ming Chen
Summary: Cu-catalyzed highly stereoselective and enantiodivergent syntheses of (Z)- or (E)-beta,?-unsaturated ketones from 1,3-butadienyl silanes are developed. The nature of the silyl group of the dienes has a significant impact on the stereo- and enantioselectivity of the reactions. The reactions result in the formation of (Z)-beta,?-unsaturated ketones with excellent enantioselectivities and high Z-selectivities or (E)-beta,?-unsaturated ketones with high optical purities and excellent E-selectivities, depending on the silyl group used.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Malavath Ratanlal, Jayaram Vankudoth, Gangavaram V. M. Sharma, Maruti A. Mali, Bertrand Carboni, Fabienne Berree, Subhash Ghosh
Summary: An efficient stereo-controlled synthesis method using sequential Suzuki-Miyaura coupling reactions from easily prepared 1-alkene-1,2-diboronic esters and alkynyl bromides to obtain enyne and enediyne derivatives is reported. The resulting enyne boronic esters were further subjected to Borono-Mannich and Suzuki coupling reactions independently to obtain a,ss-unsaturated aminoester and tri-substituted olefin derivatives, respectively. Additionally, divergent syntheses of triazole and cyclopropylboronate derivatives were also presented.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Su Hyeon Park, Sunwoo Lee
Summary: In this study, the selective synthesis of (Z)- and (E)-ss-fluoro-alpha, ss-unsaturated amides via palladium-catalyzed aminocarbonylation of 1-fluoro-2,2-diiodovinylarenes is described. The choice of catalyst and base, as well as the substitution on the phenyl ring, have a significant impact on the selectivity and yield of the products.
Article
Chemistry, Organic
Wenchao Gao, Beibei Li, Luyi Zong, Lintao Yu, Xuyang Li, Qiyang Li, Xu Zhang, Sheng Zhang, Kun Xu
Summary: An electrochemical oxidative tandem cyclization of unsaturated oximes with diselenides has been developed, providing a general access to seleno isoxazolines containing a quaternary carbon center (35 examples). This novel protocol features mild reaction conditions (metal- and oxidant-free), good functional group tolerance, and promising scalability, with plausible reaction pathways proposed.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Ze-Yin Meng, Cheng-Tao Feng, Ling Zhang, Qing Yang, De-Xiang Chen, Kun Xu
Summary: This method utilizes electrochemical conditions and ultrasonic irradiation to achieve regioselective C-H phosphorothiolation of (hetero)arenes with thiocyanate as the S source, showing wide substrate scope and advantages in green synthesis.
Article
Chemistry, Multidisciplinary
Yangye Jiang, Kun Xu, Chengchu Zeng
Summary: This study reports a new strategy for homolysis of Si-H bonds using electrooxidation, photoinduced ligand-to-metal charge transfer, and radical-mediated hydrogen atom transfer. This method provides rapid access to Si-functionalized benzimidazo-fused isoquinolinones with broad functional-group compatibility.
Article
Chemistry, Multidisciplinary
Zhoumei Tan, Xinrui He, Kun Xu, Chengchu Zeng
Summary: This study reports a new electrophotocatalytic strategy to access alkyl radicals from strong C(sp(3))-H bonds, which can be applied in Minisci alkylation reactions without the use of chemical oxidants. This method realizes the direct Minisci alkylation reaction from abundant unactivated alkanes with high atom economy.
Review
Chemistry, Multidisciplinary
Xu Cheng, Aiwen Lei, Tian-Sheng Mei, Hai-Chao Xu, Kun Xu, Chengchu Zeng
Summary: This review presents recent advances in electrochemical homogeneous catalysis, with a focus on electrochemical noble-transition-metal catalysis, photoelectrochemical catalysis, and electrochemical enantioselective catalysis. The topics discussed include the mechanism of noble metal catalysts in the presence of cathodic hydrogen evolution, the enhancement of redox properties in photocatalysis, and the regulation of enantioselectivity in catalytic electrochemical reactions.
Article
Chemistry, Organic
Zhoumei Tan, Fang Xiang, Kun Xu, Chengchu Zeng
Summary: This paper reports a new method for the hydroazolylation of alkenes with azoles under external oxidant-free conditions with low catalyst loadings.
Article
Chemistry, Organic
Shang-Feng Yang, Pei Li, Zi-Lin Fang, Sen Liang, Hong-Yu Tian, Bao-Guo Sun, Kun Xu, Cheng-Chu Zeng
Summary: The electrochemical synthesis of 2-aminothiazoles from active methylene ketones and thioureas assisted by ᴅʟ-alanine using NH4I as a redox mediator has been successfully achieved. The reaction is carried out in an undivided cell with graphite plate electrodes under constant current conditions, resulting in the conversion of various active methylene ketones to the corresponding 2-aminothiazoles. The proposed mechanism involves the in situ generated alpha-iodoketone as the key active species.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Review
Chemistry, Organic
Haonan Zhang, Sen Liang, Dengchao Wei, Kun Xu, Chengchu Zeng
Summary: This review highlights the main achievements in the field of electrocatalytic generation of acyl radicals and their applications. The electrochemical strategies are discussed in terms of substrate scope, reaction limitation, and underlying mechanism. The related reactions are categorized based on the pathways of acyl radical generation, including outer-sphere electron transfer (ET), inner-sphere ET, and hydrogen atom transfer (HAT) processes.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Fei Lian, Kun Xu, Chengchu Zeng
Summary: A new catalytic paradigm combining sequential paired electrosynthesis with halogen-bonding activation was designed for the cyclization of organochlorides with olefins, resulting in the rapid synthesis of densely functionalized 2-alkylidene-tetrahydrofurans with exclusive Z-selectivities. The use of 4,4'-di-tert-butyl-2,2'-bipyridine as a halogen-bond acceptor enabled the activation of C-Cl bonds at lowered electrode potentials. This strategy allowed for broad functional group tolerance, as demonstrated by the late-stage functionalization of various drugs and natural products-derived alkenes.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Applied
Heng-Tong Qu, Zeng-Hui Wu, Guo-Chen Zhong, Yan-Chun Zhang, Cheng-Tao Feng, Kun Xu
Summary: An aerobic Mn(III)-catalyzed one-pot three-component synthesis of 5-cyano-pyrazolo[1,5-a]pyrimidines has been developed, which relies on the synergistic combination of Strecker reaction and oxidatively-induced 6 pi-azacyclization. This protocol offers a step-economic, regioselective, and functionally tolerant strategy to obtain 5-cyano-pyrazolo[1,5-a]pyrimidines, distinct from previous reports using toxic cyanating agents or multistep synthesis.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Fei Lian, Feixian Luo, Meng Wang, Kun Xu, Chengchu Zeng
Summary: A new electrochemical strategy utilizing paired electrolysis and halogen bonding activation has been developed for the atom transfer radical addition (ATRA) of polychloroalkanes across olefins. By employing readily accessible 4,4-di-tert-butyl bipyridine (dtbpy) as a halogen bonding acceptor, the reduction potential of C-Cl bonds could be positively shifted by 110 mV. This approach allows for a wide substrate scope and excellent functional group compatibility, enabling the addition of various terminal and internal alkenes.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Organic
Wang Huiqiao, Xu Kun
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Huiqiao Wang, Ruoyu Liu, Qi Sun, Kun Xu
Summary: In this study, the successful metal-free alkylation of quinoxalinones with electron-deficient alkenes was achieved through sequential paired electrolysis. This mechanistically distinct approach provides a new method for synthesizing C-3 alkylated quinoxalinones that are difficult to prepare by other means.
CHEMICAL COMMUNICATIONS
(2023)
Review
Chemistry, Multidisciplinary
Xia Peng, Kun Xu, Qian Zhang, Li Liu, Jiajing Tan
Summary: Post-translational modifications of peptides and proteins have a significant impact on therapeutic discoveries and disruptive innovations in synthetic organic chemistry and chemical biology. Recent progress in this field includes the development of green and sustainable photocatalytic tools, particularly visible-light-driven radical conjugate addition reactions, which have advanced the synthesis of unnatural amino acids and bioconjugation chemistry. This article provides a comprehensive overview of dehydroamino acid modification, aiming to inspire future discoveries.
TRENDS IN CHEMISTRY
(2022)
Article
Chemistry, Organic
Han Qun, Xu Kun, Tian Faning, Huang Shengyang, Zeng Chengchu
Summary: A mild and scalable method using NH3·H2O for the N-deacylation of amides has been developed, which can efficiently release free amines. This method has good functional group compatibility, operational simplicity, and cost effectiveness, making it an ideal choice for N-deacylation of amides.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2022)
