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Synthesis and characterization of new ionic liquid-based Pd(II) and Pt(II) complexes of phosphinite: Use of palladium(II) complexes as pre-catalyst in Suzuki–Miyaura and Mizoroki-Heck cross-coupling reactions 新型离子液体Pd（II）和Pt（II）配合物的合成与表征：钯（II）配合物作为预催化剂在Suzuki-Miyaura和Mizoroki-Heck交叉偶联反应中的应用
IF 2.2 3区 化学
Tetrahedron Pub Date : 2026-06-01 Epub Date: 2026-02-04 DOI: 10.1016/j.tet.2026.135180
Nurgeldi Sanabay , Nermin Meri̇ç , Cezmi Kayan , Aigül Kerimkulova , Khadichakhan Rafikova , Madina Kozhaisakova , Bagadat Selenova , Murat Aydemir
{"title":"Synthesis and characterization of new ionic liquid-based Pd(II) and Pt(II) complexes of phosphinite: Use of palladium(II) complexes as pre-catalyst in Suzuki–Miyaura and Mizoroki-Heck cross-coupling reactions","authors":"Nurgeldi Sanabay ,&nbsp;Nermin Meri̇ç ,&nbsp;Cezmi Kayan ,&nbsp;Aigül Kerimkulova ,&nbsp;Khadichakhan Rafikova ,&nbsp;Madina Kozhaisakova ,&nbsp;Bagadat Selenova ,&nbsp;Murat Aydemir","doi":"10.1016/j.tet.2026.135180","DOIUrl":"10.1016/j.tet.2026.135180","url":null,"abstract":"<div><div>The palladium-catalyzed Suzuki–Miyaura and Mizoroki-Heck cross-coupling reactions are powerful tools to prepare unsymmetrical biaryl and stilbene compounds, which have been used in different areas, such as herbicides and natural product synthesis. Hence, four new Pd(II) and Pt(II) complexes (<strong>5</strong>–<strong>8</strong>) of the phosphinite ligands based on ionic liquid were synthesized. All complexes were isolated as analytically pure substances and characterized by multinuclear NMR and IR spectroscopy, and elemental analysis. The catalytic activity of palladium complexes <strong>5</strong> and <strong>6</strong> was investigated in Suzuki–Miyaura and Mizoroki-Heck cross-coupling reactions in homogeneous catalysis. The complexes were highly active catalysts in coupling a series of aryl halides with phenylboronic acid under optimum conditions in water, giving rise to turnover frequency up to 47040 h<sup>−1</sup> in Suzuki-Miyaura coupling reactions. Short reaction times with good to excellent yields of the desired products express the effectiveness of this catalyst in these reactions. Furthermore, the palladium complexes also displayed good catalytic activity in Mizoroki-Heck reaction affording <em>trans</em>-stilbenes.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"194 ","pages":"Article 135180"},"PeriodicalIF":2.2,"publicationDate":"2026-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146185796","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}
引用次数: 0
Visible-light induced three-component cascade radical sulfonation/cyclization/dearomatization: access to sulfonated spiro[5.5] trienones 可见光诱导的三组分级联自由基磺化/环化/脱芳化：获得磺化螺[5.5]三烯酮
IF 2.2 3区 化学
Tetrahedron Pub Date : 2026-06-01 Epub Date: 2026-02-11 DOI: 10.1016/j.tet.2026.135152
Dong Xia , Yanfeng Miao , Wenchao Yang , Xiaobo Bao , Jianfei Kong
{"title":"Visible-light induced three-component cascade radical sulfonation/cyclization/dearomatization: access to sulfonated spiro[5.5] trienones","authors":"Dong Xia ,&nbsp;Yanfeng Miao ,&nbsp;Wenchao Yang ,&nbsp;Xiaobo Bao ,&nbsp;Jianfei Kong","doi":"10.1016/j.tet.2026.135152","DOIUrl":"10.1016/j.tet.2026.135152","url":null,"abstract":"<div><div>A new facile visible-light induced three-component cascade radical sulfonation/cyclization/dearomatization reaction of biaryl ynones with diaryliodonium salts and DABSO was developed. Under metal free conditions, diversified sulfonated spiro[5.5]trienones were prepared with readily available diaryliodonium salts catalyzed by Eosin Y.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"194 ","pages":"Article 135152"},"PeriodicalIF":2.2,"publicationDate":"2026-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146185858","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}
引用次数: 0
Cu(II)-mediated oxidative cyclization of azocoumarins to N2-1,2,3-chromenotriazoles: Synthesis and structural characterization Cu（II）介导偶氮香豆素氧化环化成n2 -1,2,3-铬基三唑：合成及结构表征
IF 2.2 3区 化学
Tetrahedron Pub Date : 2026-06-01 Epub Date: 2026-02-04 DOI: 10.1016/j.tet.2026.135176
Fernando Alves Barretto , Micael Rodrigues Macedo , Mariana Teles de Carvalho , Carolina Bastos Pereira Ligiero , Camilla Djenne Buarque
{"title":"Cu(II)-mediated oxidative cyclization of azocoumarins to N2-1,2,3-chromenotriazoles: Synthesis and structural characterization","authors":"Fernando Alves Barretto ,&nbsp;Micael Rodrigues Macedo ,&nbsp;Mariana Teles de Carvalho ,&nbsp;Carolina Bastos Pereira Ligiero ,&nbsp;Camilla Djenne Buarque","doi":"10.1016/j.tet.2026.135176","DOIUrl":"10.1016/j.tet.2026.135176","url":null,"abstract":"<div><div>An efficient two-step synthetic protocol was developed for the preparation of N<sup>2</sup>-1,2,3-cromenonetriazole derivatives. The strategy utilizes a diazo coupling between amino coumarins and aryl diazonium salts to afford azocoumarin intermediates in 38–92% yields. These intermediates subsequently undergo Cu(OAc)<sub>2</sub>-mediated oxidative cyclization to construct the fused triazole ring, providing the final products in 10–53% yields. X-ray crystallographic analysis of a key azocoumarin revealed a predominant enamine tautomer, supported by a six-membered intramolecular hydrogen bond. This study establishes a well-characterized library of these unique heterocyclic scaffolds.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"194 ","pages":"Article 135176"},"PeriodicalIF":2.2,"publicationDate":"2026-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146185793","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}
引用次数: 0
Propylphosphonic anhydride (T3P®)-mediated multicomponent reactions 丙基磷酸酐（T3P®）介导的多组分反应
IF 2.2 3区 化学
Tetrahedron Pub Date : 2026-06-01 Epub Date: 2026-01-23 DOI: 10.1016/j.tet.2026.135157
Mátyás Milen, Patrik Pollák, Balázs Volk
{"title":"Propylphosphonic anhydride (T3P®)-mediated multicomponent reactions","authors":"Mátyás Milen,&nbsp;Patrik Pollák,&nbsp;Balázs Volk","doi":"10.1016/j.tet.2026.135157","DOIUrl":"10.1016/j.tet.2026.135157","url":null,"abstract":"<div><div>These days, multicomponent reactions, involving at least three reagents, are of particular interest for the reason that they ensure operational simplicity, and make possible the fast establishment of molecular libraries for biological screening. On the other hand, the use of propylphosphonic anhydride (T3P® reagent) as an activating agent in a wide range of organic reactions is an excellent tool. In this review article, the two above-mentioned disciplines are combined: the applications of the T3P® reagent in multicomponent organic chemical transformations are surveyed. The compilation embraces the synthesis of α-aminonitriles, α-aminoamides, α-aminophosphonates, isoindolinone-phosphonates, hydroxynaphthalenes and naphthoxazinones, pyrano- and furano-quinolines, quinazolinones, oxoisoindoline-carboxamides, imidazopyridines, thiazolidinones, dihydropyrimidinones and hexahydrodibenzodiazepinones. Comparisons with the previous preparative methods are also provided. Finally, the beneficial effect of the T3P® reagent is illustrated via the proposed mechanisms.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"194 ","pages":"Article 135157"},"PeriodicalIF":2.2,"publicationDate":"2026-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146071017","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}
引用次数: 0
Greener preparation and reactivity of diazo compounds: Moving from harmful chemistry to more environmentally benign methods 重氮化合物的绿色制备和反应性：从有害化学转向更环保的方法
IF 2.2 3区 化学
Tetrahedron Pub Date : 2026-06-01 Epub Date: 2026-01-24 DOI: 10.1016/j.tet.2026.135159
Marcus M. Sá
{"title":"Greener preparation and reactivity of diazo compounds: Moving from harmful chemistry to more environmentally benign methods","authors":"Marcus M. Sá","doi":"10.1016/j.tet.2026.135159","DOIUrl":"10.1016/j.tet.2026.135159","url":null,"abstract":"<div><div>There is an urgent need to mitigate environmental problems caused by uncontrolled human activities. The ever-increasing demand for more sustainable processes has stimulated the adoption of efficient synthetic strategies founded on the principles of green chemistry, which must be simple, safe, highly productive, and environmentally benign. Therefore, this Review showcases the most prominent achievements in the green preparation and synthetic applications of diazo compounds that were published in the last 15 years (from 2010 to middle 2025). The main approaches include the use of heterogeneous catalysis, biocatalysis, and catalyst-free protocols, the preference for water and other harmless solvents, and the search for simple and mild reaction conditions to furnish the target compounds with broad structural diversity and excellent functional group tolerance, as well as high yield and selectivity.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"194 ","pages":"Article 135159"},"PeriodicalIF":2.2,"publicationDate":"2026-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146071019","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}
引用次数: 0
Hantzsch-type regioselective synthesis of novel pentaza-5H-cyclopenta[b]anthracene-4,6-diones based on 7-(phenylamino)-[1,2,4]triazolo[4,3-a]pyrimidin-5-ones precursors 以7-（苯胺）-[1,2,4]三唑[4,3-a]嘧啶-5-酮为前体的新型五氢环五[b]蒽-4,6-二酮的hantzsch型区域选择性合成
IF 2.2 3区 化学
Tetrahedron Pub Date : 2026-06-01 Epub Date: 2026-02-10 DOI: 10.1016/j.tet.2026.135183
Mirna T. Helmy , Hamdi M. Hassaneen , Ismail A. Abdelhamid , Ehab M. Zayed , Yara N. Laboud
{"title":"Hantzsch-type regioselective synthesis of novel pentaza-5H-cyclopenta[b]anthracene-4,6-diones based on 7-(phenylamino)-[1,2,4]triazolo[4,3-a]pyrimidin-5-ones precursors","authors":"Mirna T. Helmy ,&nbsp;Hamdi M. Hassaneen ,&nbsp;Ismail A. Abdelhamid ,&nbsp;Ehab M. Zayed ,&nbsp;Yara N. Laboud","doi":"10.1016/j.tet.2026.135183","DOIUrl":"10.1016/j.tet.2026.135183","url":null,"abstract":"<div><div>We report an efficient Hantzsch-like multi-component strategy for synthesizing pentaza-5<em>H</em>-cyclopenta[<em>b</em>]anthracene-4,6-dione derivatives using 7-(phenylamino)-[1,2,4]triazolo[4,3-<em>a</em>]pyrimidin-5-ones precursors. Structural confirmation was achieved <em>via</em> two-dimensional heteronuclear multiple-bond correlation (2D-HMBC) spectroscopy, excluding regioisomeric alternatives. Mechanistic studies revealed Michael addition and cyclization pathways. An alternative alkylation route provided high yields and structural diversity, highlighting the potential of these heterocycles for biological applications.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"194 ","pages":"Article 135183"},"PeriodicalIF":2.2,"publicationDate":"2026-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146185792","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}
引用次数: 0
Direct access to α-amino amides via oxidative cleavage of alkenes 通过氧化裂解烯烃直接获得α-氨基酰胺
IF 2.2 3区 化学
Tetrahedron Pub Date : 2026-06-01 Epub Date: 2026-02-13 DOI: 10.1016/j.tet.2026.135187
Jing Li, Fengyu Huang, Qiqi Yin, Xiaoxiao Ru
{"title":"Direct access to α-amino amides via oxidative cleavage of alkenes","authors":"Jing Li,&nbsp;Fengyu Huang,&nbsp;Qiqi Yin,&nbsp;Xiaoxiao Ru","doi":"10.1016/j.tet.2026.135187","DOIUrl":"10.1016/j.tet.2026.135187","url":null,"abstract":"<div><div>A mild and efficient metal-free oxidative Ugi-type reaction strategy is reported for the synthesis of terpenoid-<em>α</em>-amino acid amide derivatives. This method employs hypervalent iodine reagents to selectively cleave the inert C<img>C double bonds in terpenoids and other alkenes, generating aza-allenium intermediates in situ that are subsequently converted into ketimine intermediates. Under mild conditions, these ketimines undergo a multicomponent reaction with isonitriles and the carboxylic acid byproducts derived from the hypervalent iodine reagents, efficiently furnishing structurally diverse <em>α</em>-amino acid amide derivatives. The reaction features a broad substrate scope, tolerating various aryl/alkyl isocyanides and hydroxyl groups, and preserves the stereochemical configuration of monoterpenoids and diterpenoids. This synthetic strategy not only expands the application of C<img>C bond cleavage in peptidomimetic synthesis but also provides a concise approach for the high-value modification of terpenoid natural products, holding significant potential in the discovery and optimization of drug lead compounds.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"194 ","pages":"Article 135187"},"PeriodicalIF":2.2,"publicationDate":"2026-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146185788","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}
引用次数: 0
Synthesis and properties of oligonucleotides containing 2′-O,4′-C-ethylene-bridged 5-methyluridines bearing a functional group on the bridge 2 ' -O,4 ' - c -乙烯桥接5-甲基尿嘧啶寡核苷酸的合成及性质
IF 2.2 3区 化学
Tetrahedron Pub Date : 2026-06-01 Epub Date: 2026-01-29 DOI: 10.1016/j.tet.2026.135160
Koichi Mizuno, Yuta Ito, Yoshiyuki Hari
{"title":"Synthesis and properties of oligonucleotides containing 2′-O,4′-C-ethylene-bridged 5-methyluridines bearing a functional group on the bridge","authors":"Koichi Mizuno,&nbsp;Yuta Ito,&nbsp;Yoshiyuki Hari","doi":"10.1016/j.tet.2026.135160","DOIUrl":"10.1016/j.tet.2026.135160","url":null,"abstract":"<div><div>2′-<em>O</em>,4′-<em>C</em>-Ethylene-bridged nucleic acid (ENA) is a promising chemical modification for oligonucleotide (ON) therapeutics. Thus, ENA analogs bearing functional groups on the ethylene bridges were designed to explore new candidates for ON therapeutics. Specifically, the phosphoramidite of 2′-<em>O</em>,4′-<em>C</em>-ethylene-bridged 5-methyluridine (ENA-T-CO<sub>2</sub>Me) bearing a methoxycarbonylmethyl group on the bridge was synthesized and it was incorporated into ONs using an automated ON synthesizer. The methoxycarbonyl moieties in the ONs were subsequently converted into carboxylic acid equivalents, such as carboxyl and carbamoyl groups, by the corresponding base treatment in a post-synthetic approach. Duplex-forming ability and nuclease stability of ONs with these ENA analogs were evaluated. Among the analogs, the carboxymethyl-substituted analog (ENA-T-CO<sub>2</sub>H) highly stabilized a duplex with single-stranded RNA and exhibited the greatest resistance to degradation by 3′-exonuclease.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"194 ","pages":"Article 135160"},"PeriodicalIF":2.2,"publicationDate":"2026-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146077003","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}
引用次数: 0
Acid-catalyzed three-component bicyclization for the synthesis of quinazoline fused imidazole-2-thione derivatives with a tetrasubstituted carbon center 酸催化三组分双环化合成四取代碳中心的喹唑啉熔融咪唑-2-硫酮衍生物
IF 2.2 3区 化学
Tetrahedron Pub Date : 2026-06-01 Epub Date: 2026-02-02 DOI: 10.1016/j.tet.2026.135172
Jiaao Xue, Kewei Hu, Duoluo Guo, Jinxing Zhang, Qun Cai
{"title":"Acid-catalyzed three-component bicyclization for the synthesis of quinazoline fused imidazole-2-thione derivatives with a tetrasubstituted carbon center","authors":"Jiaao Xue,&nbsp;Kewei Hu,&nbsp;Duoluo Guo,&nbsp;Jinxing Zhang,&nbsp;Qun Cai","doi":"10.1016/j.tet.2026.135172","DOIUrl":"10.1016/j.tet.2026.135172","url":null,"abstract":"<div><div>An acid-catalyzed three-component bicyclization strategy has been developed for constructing novel 3,9-dihydroimidazo[5,1-<em>b</em>]quinazoline-1(2<em>H</em>)-thione derivatives from readily available arylglyoxal monohydrates, 2-aminobenzylamine, and isothiocyanates. This process results in the formation of four new C–N bonds, two rings, and a tetrasubstituted carbon center with a hydroxy group in one pot. Mechanistic experiments prove that this reaction involved two-pathway cascade convergence. Moreover, a series of derivatization experiments of products have demonstrated their broad potential in synthetic applications.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"194 ","pages":"Article 135172"},"PeriodicalIF":2.2,"publicationDate":"2026-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146185806","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}
引用次数: 0
Palladium-catalyzed aminocarbonylation of vinyl bromides with formic acid and carbodiimides to access α,β-Unsaturated amides 钯催化的溴乙烯基与甲酸和碳二亚胺的氨基羰基化反应得到α，β-不饱和酰胺
IF 2.2 3区 化学
Tetrahedron Pub Date : 2026-05-01 Epub Date: 2026-01-06 DOI: 10.1016/j.tet.2026.135132
Zhaobo Fu , Zhaonian Zhang , Qian Zhang , Zeguo Fang , Dong Li
{"title":"Palladium-catalyzed aminocarbonylation of vinyl bromides with formic acid and carbodiimides to access α,β-Unsaturated amides","authors":"Zhaobo Fu ,&nbsp;Zhaonian Zhang ,&nbsp;Qian Zhang ,&nbsp;Zeguo Fang ,&nbsp;Dong Li","doi":"10.1016/j.tet.2026.135132","DOIUrl":"10.1016/j.tet.2026.135132","url":null,"abstract":"<div><div>A novel palladium-catalyzed aminocarbonylation of vinyl bromides with formic acid and carbodiimides has been developed, providing direct access to <em>α,β</em>-unsaturated amides under CO-free conditions. This transformation is enabled by a substrate-interchange strategy that integrates the complementary features of two previously reported aminocarbonylation systems. The protocol exhibits a broad substrate scope, tolerating both <em>α</em>- and <em>β</em>-bromoalkenes as well as a variety of functional groups, and can be readily scaled to gram quantities. Mechanistic studies suggest that the transformation proceeds via an ionic pathway.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"193 ","pages":"Article 135132"},"PeriodicalIF":2.2,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922701","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}
引用次数: 0
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