Pub Date : 2025-02-28DOI: 10.1016/j.tet.2025.134566
Ludmila A. Oparina, Anton V. Kuzmin, Lyudmila A. Grishchenko, Nikita A. Kolyvanov, Igor’ A. Ushakov, Boris A. Trofimov
The reactions of acylpropargylic alcohols with 1-pyrrolines (60 °C, 2−3 h) afford the acylethenyltetrahydropyrrolo[2,1-b]oxazoles and furan-3(2H)-ylideneaminoalkanones in 55–76 % and in trace to 12 % yields, respectively. Quantum-chemical calculations (B2PLYP-D3) show that formation of pyrrolo[2,1-b]oxazoles is kinetically more preferable than that of furan-3(2H)-imines, the latter being formed through 1,3(4)-dipole and 2-hydroxypyrrolidine intermediates.
{"title":"Reaction of acylpropargylic alcohols with 1-pyrrolines: A synthetic and quantum-chemical study","authors":"Ludmila A. Oparina, Anton V. Kuzmin, Lyudmila A. Grishchenko, Nikita A. Kolyvanov, Igor’ A. Ushakov, Boris A. Trofimov","doi":"10.1016/j.tet.2025.134566","DOIUrl":"10.1016/j.tet.2025.134566","url":null,"abstract":"<div><div>The reactions of acylpropargylic alcohols with 1-pyrrolines (60 °C, 2−3 h) afford the acylethenyltetrahydropyrrolo[2,1-<em>b</em>]oxazoles and furan-3(2<em>H</em>)-ylideneaminoalkanones in 55–76 % and in trace to 12 % yields, respectively. Quantum-chemical calculations (B2PLYP-D3) show that formation of pyrrolo[2,1-<em>b</em>]oxazoles is kinetically more preferable than that of furan-3(2<em>H</em>)-imines, the latter being formed through 1,3(4)-dipole and 2-hydroxypyrrolidine intermediates.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"177 ","pages":"Article 134566"},"PeriodicalIF":2.1,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143552741","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-27DOI: 10.1016/j.tet.2025.134568
Feng Wang , Sheng-Bin Wang , Jia-Qi Pan , Qiu-Yu Ma , Mingshu Wu , Rui Ning
A mild and efficient one-pot reaction for constructing benzofuro[3,2-c]quinolinones from 3-chlorooxindoles and salicylaldehydes is presented. The method involves the base-mediated formation of a dihydrobenzofuran spirooxindole intermediate, which is subsequently converted into benzofuro[3,2-c]quinolinones facilitated by TfOH. This strategy is characterized by transition metal-free conditions, easily accessible starting materials, and a broad substrate scope.
{"title":"Synthesis of benzofuro[3,2-c]quinolinones via one-pot reaction of 3-chlorooxindoles and salicylaldehydes","authors":"Feng Wang , Sheng-Bin Wang , Jia-Qi Pan , Qiu-Yu Ma , Mingshu Wu , Rui Ning","doi":"10.1016/j.tet.2025.134568","DOIUrl":"10.1016/j.tet.2025.134568","url":null,"abstract":"<div><div>A mild and efficient one-pot reaction for constructing benzofuro[3,2-c]quinolinones from 3-chlorooxindoles and salicylaldehydes is presented. The method involves the base-mediated formation of a dihydrobenzofuran spirooxindole intermediate, which is subsequently converted into benzofuro[3,2-c]quinolinones facilitated by TfOH. This strategy is characterized by transition metal-free conditions, easily accessible starting materials, and a broad substrate scope.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"177 ","pages":"Article 134568"},"PeriodicalIF":2.1,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143534097","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-26DOI: 10.1016/j.tet.2025.134556
Hui Qin , Guo-Liang Wei , Fu-Wei Wang , Xiao-Hong Mao , Mei-Hua Bao , Yi-Wen Zhang , Ping Huang , Xiao-Wei Zheng
Herein, a practical and efficient method for fluorinating various indolin-2-ones under mild conditions was presented, utilizing selectfluor as a cost-effective fluorination reagent. Notably, the protocol operated under environmentally friendly conditions, facilitating the generation of various substituted indolin-2-ones into corresponding fluorinated indolin-2-ones in moderate to good yields, all without the need for an alkali source or heating.
{"title":"3-Fluorooxindoles from indolin-2-ones by Selectfluor","authors":"Hui Qin , Guo-Liang Wei , Fu-Wei Wang , Xiao-Hong Mao , Mei-Hua Bao , Yi-Wen Zhang , Ping Huang , Xiao-Wei Zheng","doi":"10.1016/j.tet.2025.134556","DOIUrl":"10.1016/j.tet.2025.134556","url":null,"abstract":"<div><div>Herein, a practical and efficient method for fluorinating various indolin-2-ones under mild conditions was presented, utilizing selectfluor as a cost-effective fluorination reagent. Notably, the protocol operated under environmentally friendly conditions, facilitating the generation of various substituted indolin-2-ones into corresponding fluorinated indolin-2-ones in moderate to good yields, all without the need for an alkali source or heating.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"178 ","pages":"Article 134556"},"PeriodicalIF":2.1,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143686419","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-25DOI: 10.1016/j.tet.2025.134559
Fatemeh Hamidi Dastjerdi, Abbas Ali Esmaeili
An efficient, catalyst-free and eco-friendly synthesis of novel pyrano[3,2-e][1,2,4]triazolo[1,5-a]pyrimidines via cyclo-condensation of [1,2,4]triazolo[1,5-a]pyrimidine-5,7(4H,6H)-dione, aromatic aldehydes, and malononitrile has been described using ‘‘On-water” concept. The use of water as a clean media, catalyst-free conditions, excellent functional group acceptance, easier product isolation/purification without column chromatography, short reaction times, and good-to-excellent yields are the remarkable privileges of this protocol. Finally, 1H, 13C NMR, IR, mass spectra, and elemental analyses were conducted to determine the products’ structure.
{"title":"Efficient on-water synthesis of novel pyrano[3,2-e][1,2,4]triazolo[1,5-a]pyrimidines via catalyst-free one-pot three-component reaction","authors":"Fatemeh Hamidi Dastjerdi, Abbas Ali Esmaeili","doi":"10.1016/j.tet.2025.134559","DOIUrl":"10.1016/j.tet.2025.134559","url":null,"abstract":"<div><div>An efficient, catalyst-free and eco-friendly synthesis of novel pyrano[3,2-<em>e</em>][1,2,4]triazolo[1,5-<em>a</em>]pyrimidines <em>via</em> cyclo-condensation of [1,2,4]triazolo[1,5-<em>a</em>]pyrimidine-5,7(4<em>H</em>,6<em>H</em>)-dione, aromatic aldehydes, and malononitrile has been described using ‘‘On-water” concept. The use of water as a clean media, catalyst-free conditions, excellent functional group acceptance, easier product isolation/purification without column chromatography, short reaction times, and good-to-excellent yields are the remarkable privileges of this protocol. Finally, <sup>1</sup>H, <sup>13</sup>C NMR, IR, mass spectra, and elemental analyses were conducted to determine the products’ structure.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"176 ","pages":"Article 134559"},"PeriodicalIF":2.1,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143511947","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-25DOI: 10.1016/j.tet.2025.134562
Shengxing Xie, Jinxia Yang, Rong Ma, Minghui Liu, Xinyuan Zhang, Neng-Fei Wang, Chengyu Wang, Lingkai Kong
An efficient transition-metal-free 1,10-phenanthroline-promoted homocoupling reaction has been developed to construct biaryl diamides from 2-iodobenzamides. Various desired products were smoothly synthesized with readily available starting materials in good to excellent yields under the standard reaction conditions. And this method showed a wide substrate scope and good functional group tolerance.
{"title":"A transition-metal-free 1,10-phenanthroline-promoted homocoupling reaction for the construction of biaryl diamides","authors":"Shengxing Xie, Jinxia Yang, Rong Ma, Minghui Liu, Xinyuan Zhang, Neng-Fei Wang, Chengyu Wang, Lingkai Kong","doi":"10.1016/j.tet.2025.134562","DOIUrl":"10.1016/j.tet.2025.134562","url":null,"abstract":"<div><div>An efficient transition-metal-free 1,10-phenanthroline-promoted homocoupling reaction has been developed to construct biaryl diamides from 2-iodobenzamides. Various desired products were smoothly synthesized with readily available starting materials in good to excellent yields under the standard reaction conditions. And this method showed a wide substrate scope and good functional group tolerance.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"176 ","pages":"Article 134562"},"PeriodicalIF":2.1,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143509831","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-24DOI: 10.1016/j.tet.2025.134560
Tasuku Ito, Xiongjie Jin, Kyoko Nozaki
Electrochemical regioselective conversion of carboxylic acids to terminal alkenes through dehydrogenative decarboxylation was developed. Mechanistic studies suggested that the reaction proceeds through oxidative decarboxylation of carboxylic acids to give the corresponding primary carbocation intermediates followed by deprotonation. It was implied that when using a supporting electrolyte with high donor number anion, such as dialkyl phosphate, the isomerization of the primary carbocation intermediates was suppressed to cause higher selectivity to terminal alkenes.
{"title":"Electrochemical conversion of carboxylic acids to terminal alkenes enabled by dialkyl phosphate electrolyte","authors":"Tasuku Ito, Xiongjie Jin, Kyoko Nozaki","doi":"10.1016/j.tet.2025.134560","DOIUrl":"10.1016/j.tet.2025.134560","url":null,"abstract":"<div><div>Electrochemical regioselective conversion of carboxylic acids to terminal alkenes through dehydrogenative decarboxylation was developed. Mechanistic studies suggested that the reaction proceeds through oxidative decarboxylation of carboxylic acids to give the corresponding primary carbocation intermediates followed by deprotonation. It was implied that when using a supporting electrolyte with high donor number anion, such as dialkyl phosphate, the isomerization of the primary carbocation intermediates was suppressed to cause higher selectivity to terminal alkenes.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"176 ","pages":"Article 134560"},"PeriodicalIF":2.1,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143511948","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-24DOI: 10.1016/j.tet.2025.134558
Xiao-Wei Han , Yuan-Shuai Wu , Tie Wu , Xue-Qiang Chu , Li-Xin Zhai , Chengping Miao , Zhi-Liang Shen
Magnesium was found to be capable of efficiently mediating the one-pot reductive cross-couplings of aryl aldehydes, aryl bromides, and pyridin-2-yl benzoates under transition metal-free conditions. The three-component reactions proceeded well at room temperature in THF in the presence of LiCl, enabling a chemoselective delivery of a large library of diarylmethanol esters in moderate to good yields with broad functionality compatibility. Apart from aryl substituted substrates which served as efficient electrophiles for the present protocol, alkyl substituted starting materials could be amenable to the reaction as well. In addition, the synthetic potency of the method is demonstrated through the scale-up synthesis and the late-stage derivatization of biologically active molecules. The method, which employed readily available starting materials and eliminated the utilization of sensitive and poorly available organometallic reagents, features simple manipulation and step-economy, potentially serving as an appealing alternative to existing methods for the access to diarylmethanol esters.
{"title":"Magnesium-mediated three-component reductive cross-couplings of aryl aldehydes, aryl bromides, and aryl 2-pyridyl esters: An efficient synthesis of diarylmethanol esters","authors":"Xiao-Wei Han , Yuan-Shuai Wu , Tie Wu , Xue-Qiang Chu , Li-Xin Zhai , Chengping Miao , Zhi-Liang Shen","doi":"10.1016/j.tet.2025.134558","DOIUrl":"10.1016/j.tet.2025.134558","url":null,"abstract":"<div><div>Magnesium was found to be capable of efficiently mediating the one-pot reductive cross-couplings of aryl aldehydes, aryl bromides, and pyridin-2-yl benzoates under transition metal-free conditions. The three-component reactions proceeded well at room temperature in THF in the presence of LiCl, enabling a chemoselective delivery of a large library of diarylmethanol esters in moderate to good yields with broad functionality compatibility. Apart from aryl substituted substrates which served as efficient electrophiles for the present protocol, alkyl substituted starting materials could be amenable to the reaction as well. In addition, the synthetic potency of the method is demonstrated through the scale-up synthesis and the late-stage derivatization of biologically active molecules. The method, which employed readily available starting materials and eliminated the utilization of sensitive and poorly available organometallic reagents, features simple manipulation and step-economy, potentially serving as an appealing alternative to existing methods for the access to diarylmethanol esters.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"176 ","pages":"Article 134558"},"PeriodicalIF":2.1,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143519911","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-21DOI: 10.1016/j.tet.2025.134552
Sandeep Kumar, Aditi Arora, Sumit Kumar, Brajendra K. Singh
A novel and highly efficient microwave-assisted palladium-catalyzed method has been developed for the regioselective ortho-acyloxylation, and ortho-hydroxylation of 3-phenyl-2H-benzo[b][1,4]oxazin-2-ones. Utilizing the C–H activation strategy, this protocol exploits the directing effect of nitrogen within the heterocyclic framework, enabling selective introduction of acetoxyl, butoxyl, and hydroxyl groups with excellent regioselectivity and moderate to good yields. The method exhibits broad substrate compatibility and impressive tolerance to various functional groups, offering significant advantages in cost-effectiveness and time efficiency, with reactions completed within minutes and easily scalable to gram quantities. Additionally, late-stage functionalization of hydroxylated compounds via the Suzuki reaction demonstrates the method's utility in drug discovery, facilitating further functionalization of biologically active molecules with outstanding regioselectivity.
{"title":"Microwave assisted N-directed Pd-catalyzed direct ortho-acyloxylation, and ortho-hydroxylation of benzo[b][1,4]oxazin- 2-ones via C–H activation","authors":"Sandeep Kumar, Aditi Arora, Sumit Kumar, Brajendra K. Singh","doi":"10.1016/j.tet.2025.134552","DOIUrl":"10.1016/j.tet.2025.134552","url":null,"abstract":"<div><div>A novel and highly efficient microwave-assisted palladium-catalyzed method has been developed for the regioselective <em>ortho</em>-acyloxylation, and <em>ortho</em>-hydroxylation of 3-phenyl-2<em>H</em>-benzo[<em>b</em>][1,4]oxazin-2-ones. Utilizing the C–H activation strategy, this protocol exploits the directing effect of nitrogen within the heterocyclic framework, enabling selective introduction of acetoxyl, butoxyl, and hydroxyl groups with excellent regioselectivity and moderate to good yields. The method exhibits broad substrate compatibility and impressive tolerance to various functional groups, offering significant advantages in cost-effectiveness and time efficiency, with reactions completed within minutes and easily scalable to gram quantities. Additionally, late-stage functionalization of hydroxylated compounds <em>via</em> the Suzuki reaction demonstrates the method's utility in drug discovery, facilitating further functionalization of biologically active molecules with outstanding regioselectivity.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"176 ","pages":"Article 134552"},"PeriodicalIF":2.1,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143509832","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-20DOI: 10.1016/j.tet.2025.134539
Ting Su , Mingfeng Li , Fanke Meng , Qinglei Chong
Enantioselective synthesis of homopropargyl amines from easily available starting materials is attractive and challenging in organic synthesis field. Herein, we reported a copper(I) hydride (Cu–H)-catalyzed reductive coupling reactions of isatin ketimines or aldimines with a broad range of 1,3-enynes bearing silyl, alkyl, aryl, heteroaryl substituents, affording a variety of homopropargyl amines in up to 98 % yield with up to >95:5 dr and >99:1 er. A single multi-functional catalyst effectively controlled the chemo-, regio-, diastereo- and enantioselectivity. Selective deprotection of the resulting enantio-enriched homopropargyl amines followed by functionalizations furnished a variety of useful building blocks.
{"title":"Copper–hydride catalyzed diastereo- and enantioselective synthesis of homopropargyl amines through reductive coupling of 1,3-enynes with imines","authors":"Ting Su , Mingfeng Li , Fanke Meng , Qinglei Chong","doi":"10.1016/j.tet.2025.134539","DOIUrl":"10.1016/j.tet.2025.134539","url":null,"abstract":"<div><div>Enantioselective synthesis of homopropargyl amines from easily available starting materials is attractive and challenging in organic synthesis field. Herein, we reported a copper(I) hydride (Cu–H)-catalyzed reductive coupling reactions of isatin ketimines or aldimines with a broad range of 1,3-enynes bearing silyl, alkyl, aryl, heteroaryl substituents, affording a variety of homopropargyl amines in up to 98 % yield with up to >95:5 dr and >99:1 er. A single multi-functional catalyst effectively controlled the chemo-, regio-, diastereo- and enantioselectivity. Selective deprotection of the resulting enantio-enriched homopropargyl amines followed by functionalizations furnished a variety of useful building blocks.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"176 ","pages":"Article 134539"},"PeriodicalIF":2.1,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143474020","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-20DOI: 10.1016/j.tet.2025.134542
Jeffrey C. Ferreira, Douglas A. Klumpp
A series of imidazole-containing fluorenyl spirocycles have been prepared from 9-fluorenol derivatives. Highly acidic media and superacid media are shown to promote spirocyclization to this new class of spirocycles. A mechanism is proposed involving fluorenyl cationic species, including dicationic ions. Electrochemical and optical experiments were conducted for the calculation of frontier molecular orbital energy levels. Fluorescence spectroscopy showed that select conjugated fluorophores were intensely emissive in the near-UV visible (blue-purple) spectrum range.
{"title":"Superacid-promoted synthesis of imidazole-containing spirocycles","authors":"Jeffrey C. Ferreira, Douglas A. Klumpp","doi":"10.1016/j.tet.2025.134542","DOIUrl":"10.1016/j.tet.2025.134542","url":null,"abstract":"<div><div>A series of imidazole-containing fluorenyl spirocycles have been prepared from 9-fluorenol derivatives. Highly acidic media and superacid media are shown to promote spirocyclization to this new class of spirocycles. A mechanism is proposed involving fluorenyl cationic species, including dicationic ions. Electrochemical and optical experiments were conducted for the calculation of frontier molecular orbital energy levels. Fluorescence spectroscopy showed that select conjugated fluorophores were intensely emissive in the near-UV visible (blue-purple) spectrum range.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"176 ","pages":"Article 134542"},"PeriodicalIF":2.1,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143509830","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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