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Chinese Journal of Chemistry 2024年第1期42卷 43-47页

作者： Li Wang Renwei Xiao Jingyuan Song Long-Sheng Zheng Qiwei Lang Gen-Qiang Chen Xumu Zhang Shenzhen Key Laboratory of Small Molecule Drug Discovery and Synthesis Department of Chemistryand Medi-PingshanSouthern University of Science and TechnologyShenzhenGuangdong 518000China Academy for Advanced Interdisciplinary Studies Southern Universityof Science and TechnologyShenzhenGuangdong 518000China Chemistry and Chemical Engineering Guangdong Laboratory ShantouGuangdong 515031China

Transition metal-catalyzed asymmetric transfer hydrogenation has been proven to be a powerful approach for the synthesis of chiral alcohols.Herein,a highly efficient and enantioselective transfer hydrogenation of dibenzoheptaheterocyclic ketones catalyzed by an arene-tethered TsDPEN-based Rh(ll)catalyst has been successfully developed,and a variety of dibenzoheptaheterocyclic ketones were reduced by a 1/1 mixture of formic acid and DBU(1,8-diazabicyclo[5.4.0]undec-7-ene)with high yields and enantioselectivities.With this method,the asymmetric reduction of 7,8-difluorodibenzo[b,e]thiepin-11(6H)-one has been realized,providing the key intermediate of baloxavir marboxil with>99% yield and>99% ee at a substrate/catalyst molar ratio of 1000.

关键词： Asymmetric transfer hydrogenation Baloxavir Chiral alcohol enantioselectivity Heterocyclic diaryl ketone Rhodium(Ⅱ)

Atroposelective Synthesis of 2-Arylindoles via Chiral Phosphoric Acid-Catalyzed Direct Amination of Indoles

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Chinese Journal of Chemistry 2024年第7期42卷 731-735页

作者： Wen Bao Ye-Hui Chen Yu-Wei Liu Shao-Hua Xiang Bin Tan School of Pharmacy&StateKey Laboratory of Applied Organic Chemistry Lanzhou UniversityLanzhouGansu 730000China Shenzhen Grubbs Institute Department of ChemistrySouthern University of Science and TechnologyShenzhenGuangdong 518055China

Indole-based atropisomers are a very important class of axially chiral compounds.However,the atroposelective synthesis of axially chiral 2-arylindole remains largely unexplored.In this study,we report the successful synthesis of atropisomeric 2-arylindoles using direct amination of indoles with p-quinonediimines in the presence of chiral phosphoric acid as a catalyst.Quinonediimine acts as an aminating reagent through formal polarity inversion of imine.The malonate group on the 2-aryl of 2-indoles was found to be essen-tial for high enantioselectivity of the products.This could be due to the additional interaction between the ester group and the cata-lyst,as well as the intramolecular hydrogen bonding.Our findings provide a new strategy for the asymmetric construction of 2-arylindole atropisomers.

关键词： Chiral phosphoric acid Quinonediimines Direct amination Nucleophilic addition Asymmetric catalysis enantioselectivity Axially chiral 2-arylindole Atroposelective synthesis

One-Pot Stereoselective Synthesis of Different Fused Multicyclic Iminosugars Based on the Iminium-lon Intermediate

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Chinese Journal of Chemistry 2024年第2期42卷 142-150页

作者： Song Xie Jilai Wu Likai Zhou Chao Wei Xiaoliu Li Hua Chen Key Laboratoryof Chemical Biology of Hebei Province College of Chemistry and Material ScienceHebei UniversityBaodingHebei 071002China College of Chemistry and Chemical Engineering Xingtai UniversityXingtaiHebei 054001China

Different novel fused multicyclic iminosugars were synthesized from D-ribose tosylate,aniline and vinyl ethyl ether by one-pot three-component stereoselective[4+2]reaction at different temperatures.The iminium-ion is the key intermediate for the reaction.As a result,several complex fused iminosugars 3a were obtained by aza-Diels-Alder mechanism at 60℃,while a series of aza-C-glycosides 5a were prepared by Mannich reaction at room temperature accompanied by another tetrahydroquinoline-fused iminosugars 4a(tricyclic derivatives)through aza-Diels-Alder cycloaddition.This strategy will help to construct structurally diverse and bioactive iminosugar analogues.

关键词： Fused multicyclic iminosugar Aza-Diels-Alder cycloaddition Mannich reaction Tetrahydroquinoline Multicomponent reactions enantioselectivity Cyclization

SO_(2)-Insertion induced enantioselective oxysulfonylation to access β-chiral sulfones with quaternary carbon stereocenters

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Science China Chemistry 2024年第3期67卷 908-913页

作者： Jun Zhang Xuefeng Wang Peiqi Wang Jiayuan Fang Shaoyu Li Jie Wu School of Pharmaceutical and Chemical Engineering&Institute for Advanced Studies Taizhou UniversityShanghai 200438China Department of Chemistry Fudan UniversityShanghai 200438China State Key Laboratory of Organometallic Chemistry Shanghai Institute of Organic ChemistryChinese Academy of SciencesShanghai 200032China School of Chemistry and Chemical Engineering Henan Normal UniversityXinxiang 453007China

β-Chiral sulfones are structural motifs widely found in natural products and bioactive molecules, while also serving as important intermediates for the synthesis of valuable chiral scaffolds. In contrast to the rapid growth of sulfur dioxide insertion chemistry over the last decade, enantioselective catalytic variants for accessing β-chiral sulfones, especially those bearing a quaternary carbon stereocenter, remain rare. Herein, we report an enantioselective copper/bisoxazoline catalyzed oxysulfonylation of alkenes to yield isoxazolinyl-containing β-chiral sulfones bearing quaternary carbon stereocenters with moderate to excellent yields and up to 96:4 er. The advantage and irreplaceability of this sulfur dioxide insertion catalytic system have been demonstrated by achieving transformations clearly unavailable with the previously reported sulfonyl chloride system. Additionally,the recoverability of the new-developed bisoxazoline ligand L9 and its reusability without any erosion of the catalytic activity and enantioselectivity further demonstrate the usefulness of the protocol.

关键词： β-chiral sulfones sulfur dioxide insertion oxysulfonylation copper catalysis enantioselectivity

Integrated separation-electrochemical detection device based on wood column for online identification of enantiomer

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Nano Research 2024年第3期17卷 1893-1901页

作者： Junli Guo Yuanfei Xue Chenxi Zhao Junjian Zhao Zhida Gao Ye Mei Yan-Yan Song College of Sciences Northeastern UniversityShenyang 110004China State Key Laboratory of Precision Spectroscopy School of Physics and Electronic ScienceEast China Normal UniversityShanghai 200062China NYU-ECNU Center for Computational Chemistry at NYU Shanghai Shanghai 200062China Collaborative Innovation Center of Extreme Optics Shanxi UniversityTaiyuan 030006China

Chiral chemicals have attracted significant interest in the pharmaceutical industry,yet the separation methods to get pure enantiomers from racemic mixture are still challenging.To date,the separation of enantiomers still mainly depends on chromatography using high-cost chiral stationary phases.Herein,wood channels were used as the handheld integrated device,and enantiomer separation was simultaneously detected using an electrochemical detector.In this method,a chiral UIO-66(L-UIO-66)modified enantiomer separation zone and carbonized wood based online detection zone are integrated along a single wood column.Based on the in situ separation results from the chronoamperometry data,the wood device shows excellent separation ability for a wide range of electrochemically active enantiomers,including 3,4-dihydroxyphenylalanine,amino acids,ascorbic acid,carnitine,and penicillamine with high chirality purity.The unbiased molecular dynamic simulations indicate that the excellent chiral recognition and separation are attributed to the different barriers from the bound states to the dissociated state of the enantiomers in the homochiral microenvironment of the framework.This integrated enantiomer separation-electrochemical detection device provides a novel,easy,and low-cost platform for the separation of pure enantiomer from racemic mixture.

关键词： wood column integrated separation-detection device enantioselectivity online sensing free energy barrier

Ni-catalyzed highly regio- and stereo-selective diborylative cyclization of 1,6-enynes with diboron reagent

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Science China Chemistry 2024年第3期67卷 981-989页

作者： Qitao Guan Zhen Shen Yiqiang Tian Genping Huang Chun Zhang Institute of Molecular Plus Tianjin Key Laboratory of Molecular Optoelectronic ScienceDepartment of ChemistrySchool of SciencesTianjin UniversityTianjin 300072China State Key Laboratory of Elemento-Organic Chemistry Nankai UniversityTianjin 300071China

The Ni-catalyzed highly selective diborylative cyclization of 1,6-enynes with diboron reagent has been developed. When pinB-Bdan was used, multiple types of boron-containing functional groups could be installed into organic molecule with great chemoselectivity and regioselectivity though this reaction. Meanwhile, if B_2pai_2 was employed, the asymmetric diborylative cyclization could be well induced by using strategy of dynamic kinetic resolution. Importantly, the above reactions could afford desired product with 100% atomic economy, and could be compatible with different series of substituents. The studies of further transformation well illustrated that different type products could serve diverse synthetic strategy. Notably, the reaction mechanism was intensively studied by density functional theory(DFT) calculations, which could reveal the mechanism of regio- and enantio-selective control.

关键词： nickel-catalyzed organoboron cyclization regioselectivity enantioselectivity

Palladium-Catalyzed[4+2]and[6+2]Dipolar Cycloadditions for the Construction of Benzo[d]isothiazole 1,1-Dioxide Fused 1,3-Oxazinanes and 1,3-Oxazocanes

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Chinese Journal of Chemistry 2024年第8期42卷 829-834页

作者： Lei Chen Hongling Xie Yu Xue Zhengyu Han Jianwei Sun Hai Huang Jiangsu Key Laboratory of Advanced Catalytic Materials&Technology School of Petrochemical EngineeringChangzhou UniversityChangzhouJiangsu213164 China Department of Chemistry The Hong Kong University of Science and TechnologyClear Water BayKowloonHong Kong SARChina

Comprehensive Summary,The Pd-catalyzed dipolar cycloaddition represents a significant synthetic strategy for the construction of useful heterocyclic compounds.This study developed the dipolar[4+2]and[6+2]cycloaddition reactions of benzo[d]isothiazole 1,1-dioxides(BDs)leading to the synthesis of BD-fused 1,3-oxazinane and 1,3-oxazocane derivatives,respectively.In particular,the synthesis of BD-fused 1,3-oxazinanes demonstrated regio-and enantioselective characteristics,resulting in products with good yields,enantioselectivity and regioselectivity(if applicable).Furthermore,the[6+2]cycloaddition reaction developed in this work represented the first strategy for the synthesis of medium-sized ring compounds based on BDs.

关键词： Cycloaddition 1,3-Oxazinanes 1,3-Oxazocanes Medium-ring compounds Stereochemistry N-Heterocycles Sulfonamides enantioselectivity Asymmetricsynthesis

Iridium-Catalyzed Site-and Enantioselective C(sp^(2))-H Borylation of Benzhydryl Ethers:enantioselectivity Amplification by Kinetic Resolution Relay

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Chinese Journal of Chemistry 2023年第17期41卷 2119-2124页

作者： Ke Jing Lili Chen Panke Zhang Senmiao Xu State Key Laboratory for Oxo Synthesis and Selective Oxidation Lanzhou Institute of Chemical PhysicsChinese Academy of SciencesLanzhouGansu 730000China Green Catalysis Center and College of ChemistryZhengzhou UniversityZhengzhouHenan 450001China

Comprehensive Summary,We herein report a simple ether-directed iridium-catalyzed site-and enantioselective C(sp^(2))-H borylation of benzhydryl ethers for the first time.Various chiral benzhydryl ethers were obtained with high enantioselectivities in the presence of a tailor-made chiral bidentate boryl ligand.We found that the kinetic resolution relay significantly amplified the enantioselectivity.The synthetic utility of the current method was demonstrated by gram-scale C—H borylation and C—B bond transformations.

关键词： Asymmetric catalysis Benzhydryl ethers C-H activation enantioselectivity Kinetic resolution

enantioselectivity of Photochemical Reactions within Polymer Microcapsules

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Chinese Journal of Chemistry 2003年第1期21卷 96-97页

作者：马磊吴骊珠张丽萍佟振合 Technical Institute of Physics and Chemistry Chinese Academy of Sciences

Polymer microcapsule was employed as a reaction medium to achieve enantioselectivity in photochemical reduction of phenyl cyclohexyl ketone and photoelectrocyclization of tropolone methyl ether under the influence of various chiral inductors. In all cases, low but evident enantioselectivity was observed. The poor enantioselectivity is probably due to the facts that not all the capsules include simultaneously both the chiral inductor and the reactant molecules, and the wall of the microcapsule is not rigid enough to hold the reactant and the chiral inductor molecules in close contact.

关键词： microcapsule enantioselectivity photochemical reduction photoelectrocyclization phenyl cyclohexyl ketone tropolone methyl ether

Using multiple site-directed modification of epoxide hydrolase to significantly improve its enantioselectivity in hydrolysis of rac-glycidyl phenyl ether

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Chinese Journal of Chemical Engineering 2020年第8期28卷 2181-2189页

作者： Yao Li Xiaoyang Ou Zewang Guo Minhua Zong Wenyong Lou Lab of Applied Biocatalysis School of Food Science and EngineeringSouth China University of TechnologyGuangzhou 510640China

The epoxide hydrolase gene(SpEH) from Sphingomonas sp. HXN-200 was synthesized and expressed in robust Escherichia coli cells that had a dual protection system. The enantioselectivity(E-value) of the recombinant SpEH was 7.7 and the yield of the remaining(R)-PGE was 24.3% for the hydrolysis of racemic phenyl glycidyl ether(rac-PGE). To improve the catalytic properties of SpEH, the site-directed mutagenesis was carried out based on homology modeling, sequence alignment and molecular docking. Six residues(V195, V196, F218,N226, Q312, and M332) near the active site were mutated to hydrophobic amino acids and the positive mutations were selected for combinatorial mutation. The optimal mutant SpEH^(V196A/N226A/M332A) had an enhanced E-value of 21.2 and a specific activity of 4.57 U·mg^-1-wet cells, which were 2.8-, and 2.3-fold higher than those of wild-type SpEH. The optimal temperature and p H for purified Sp EHV196 A/N226 A/M332 Ato catalyze the hydrolysis of rac-PGE were 25 ℃ and 7.0 with 200 U·mg^-1. The enantioselectivity and yield of the remaining(R)-PGE of E. coliSpEH^(V196A/N226A/M332A)increased from 7.7 to 21.2 and 24.3% to 40.9%, respectively. The molecular docking and kinetic parameter analyses showed that SpEH^(V196A/N226A/M332A) has a greater affinity toward(S)-PGE than(R)-PGE, and that it was more difficult for the O-atom of ASP170 to achieve the nucleophilic attack on the Cα of(R)-PGE, resulting in its improved enantioselectivity.

关键词： Epoxide hydrolase Phenyl glycidyl ether enantioselectivity Directed modification