Pub Date : 2026-01-15Epub Date: 2025-11-14DOI: 10.1016/j.tet.2025.135060
Yuanfang Liu , Ruiying Pan , Xinni Xie , Jun Liu , Yuguo Du
A series of novel petrosiol E derivatives were synthesized by divergent strategies starting from readily available d-xylose as the chiral template. The pro-differentiating capacities of these derivatives were evaluated using a differentiation model of rat neuron-like PC12 cells and several derivatives exhibited moderate to significant pro-differentiating capacities. Our study demonstrated that the pro-differentiating capacities of these derivatives were very sensitive to modifications in the side chains, suggesting that the conjugated diyne skeleton and terminal alkyl residue might play important roles in the neuronal differentiation.
{"title":"Design, synthesis, and evaluation of petrosiol E derivatives on neuronal progenitors differentiation","authors":"Yuanfang Liu , Ruiying Pan , Xinni Xie , Jun Liu , Yuguo Du","doi":"10.1016/j.tet.2025.135060","DOIUrl":"10.1016/j.tet.2025.135060","url":null,"abstract":"<div><div>A series of novel petrosiol E derivatives were synthesized by divergent strategies starting from readily available <span>d</span>-xylose as the chiral template. The pro-differentiating capacities of these derivatives were evaluated using a differentiation model of rat neuron-like PC12 cells and several derivatives exhibited moderate to significant pro-differentiating capacities. Our study demonstrated that the pro-differentiating capacities of these derivatives were very sensitive to modifications in the side chains, suggesting that the conjugated diyne skeleton and terminal alkyl residue might play important roles in the neuronal differentiation.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"190 ","pages":"Article 135060"},"PeriodicalIF":2.2,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145577159","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}
The low steric hindrance of small-substituent 2,4-diketones presents a significant challenge for effective asymmetric induction.An efficient and highly enantioselective catalytic system was developed for the Biginelli reaction to access chiral 4,5,6-trisubstituted-3,4-dihydropyrimidinethiones. Through catalyst screening, chiral imidodiphosphoric acid was found to outperform conventional chiral phosphoric acids. Under the optimized conditions, up to 99 % ee and 52–92 % isolated yields were achieved. This method offers a valuable strategy for the asymmetric synthesis of bioactive pyrimidine derivatives with potential pharmaceutical applicatioins.
{"title":"Asymmetric synthesis of chiral 4,5,6-trisubstituted-3,4-dihydropyrimidinethiones catalyzed by chiral Brønsted acid","authors":"Lingkai Kong, Zhe Li, Chunzhi Ju, Peng Wang, Guangliang Zhang, Suoqin Zhang","doi":"10.1016/j.tet.2025.134999","DOIUrl":"10.1016/j.tet.2025.134999","url":null,"abstract":"<div><div>The low steric hindrance of small-substituent 2,4-diketones presents a significant challenge for effective asymmetric induction.An efficient and highly enantioselective catalytic system was developed for the Biginelli reaction to access chiral 4,5,6-trisubstituted-3,4-dihydropyrimidinethiones. Through catalyst screening, chiral imidodiphosphoric acid was found to outperform conventional chiral phosphoric acids. Under the optimized conditions, up to 99 % ee and 52–92 % isolated yields were achieved. This method offers a valuable strategy for the asymmetric synthesis of bioactive pyrimidine derivatives with potential pharmaceutical applicatioins.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"190 ","pages":"Article 134999"},"PeriodicalIF":2.2,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145384501","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 : 2026-01-15Epub Date: 2025-11-12DOI: 10.1016/j.tet.2025.135057
Jiahong Chen, Yuanyuan Huang, Nan Wang, You Zi
A practical and N-selective allylation of sulfenamides using Morita-Baylis-Hillman carbonates under Lewis base catalysis is reported. It features broad substrate scope, high chemoselectivity, and tolerance to various functional groups, affording diverse N-allylated sulfenamides in good to excellent yields. Gram-scale experiments confirm its scalability, facilitating the synthesis of bioactive molecules and expanding the utility of sulfenamide chemistry.
{"title":"Lewis base catalyzed N-selective allylation of sufenamides with Morita–Baylis–Hillman carbonates","authors":"Jiahong Chen, Yuanyuan Huang, Nan Wang, You Zi","doi":"10.1016/j.tet.2025.135057","DOIUrl":"10.1016/j.tet.2025.135057","url":null,"abstract":"<div><div>A practical and N-selective allylation of sulfenamides using Morita-Baylis-Hillman carbonates under Lewis base catalysis is reported. It features broad substrate scope, high chemoselectivity, and tolerance to various functional groups, affording diverse N-allylated sulfenamides in good to excellent yields. Gram-scale experiments confirm its scalability, facilitating the synthesis of bioactive molecules and expanding the utility of sulfenamide chemistry.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"190 ","pages":"Article 135057"},"PeriodicalIF":2.2,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145526717","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 : 2026-01-15Epub Date: 2025-10-28DOI: 10.1016/j.tet.2025.135027
Zhen-Ye Wu , Jiang-Hong Liu , Qing Liu , Li Hai , Zhong-Zhen Yang , Yong Wu
Under visible-light irradiation, a metal-free photocatalytic system enables the generation of reactive silicon-centered radicals from a silicate reagent. The radicals undergo efficient addition to olefins, followed by polarity inversion, elimination of the leaving group, and strain-driven cyclization to afford cyclopropane-functionalized silicon products. Notably, this protocol avoids transition-metal catalysts and exhibits broad functional group tolerance. The reaction provides a sustainable strategy for constructing strained carbocycles under mild conditions.
{"title":"Photoinduced cyclopropanation of olefins via silicoborate-mediated radical transfer","authors":"Zhen-Ye Wu , Jiang-Hong Liu , Qing Liu , Li Hai , Zhong-Zhen Yang , Yong Wu","doi":"10.1016/j.tet.2025.135027","DOIUrl":"10.1016/j.tet.2025.135027","url":null,"abstract":"<div><div>Under visible-light irradiation, a metal-free photocatalytic system enables the generation of reactive silicon-centered radicals from a silicate reagent. The radicals undergo efficient addition to olefins, followed by polarity inversion, elimination of the leaving group, and strain-driven cyclization to afford cyclopropane-functionalized silicon products. Notably, this protocol avoids transition-metal catalysts and exhibits broad functional group tolerance. The reaction provides a sustainable strategy for constructing strained carbocycles under mild conditions.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"190 ","pages":"Article 135027"},"PeriodicalIF":2.2,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145415049","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 : 2026-01-15Epub Date: 2025-10-18DOI: 10.1016/j.tet.2025.135000
Junyang Tang , Yaorong Liu , Baojie Qiu , Chun He , Xingxian Zhang
A palladium-catalyzed arene ortho C–H chlorination of 4-aryl-pyrrolo[2,3-d]pyrimidines has been developed using inexpensive p-toluenesulfonyl chloride (TsCl) as a practical chlorine source. This transformation endows facile fabrication of C–Cl bond with high regioselectivity and wide functional group tolerance exploiting directing properties of pyrimidinic nitrogen on pharmacodynamic 7-deazapurines. The synthetic utility of this protocol is demonstrated through gram-scale synthesis and diverse late-stage functionalization.
{"title":"Pd-catalyzed site-selective arene ortho C–H chlorination of 4-aryl-pyrrolo[2,3-d]pyrimidines with para- toluenesulfonylchloride","authors":"Junyang Tang , Yaorong Liu , Baojie Qiu , Chun He , Xingxian Zhang","doi":"10.1016/j.tet.2025.135000","DOIUrl":"10.1016/j.tet.2025.135000","url":null,"abstract":"<div><div>A palladium-catalyzed arene <em>ortho</em> C–H chlorination of 4-aryl-pyrrolo[2,3-<em>d</em>]pyrimidines has been developed using inexpensive <em>p</em>-toluenesulfonyl chloride (TsCl) as a practical chlorine source. This transformation endows facile fabrication of C–Cl bond with high regioselectivity and wide functional group tolerance exploiting directing properties of pyrimidinic nitrogen on pharmacodynamic 7-deazapurines. The synthetic utility of this protocol is demonstrated through gram-scale synthesis and diverse late-stage functionalization.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"190 ","pages":"Article 135000"},"PeriodicalIF":2.2,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145415047","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 : 2026-01-15Epub Date: 2025-10-31DOI: 10.1016/j.tet.2025.135036
Quanlin Wu , Can Yang , Xinying Man , Xin Li , Quansen Wu , Yijing Zhang , Dongfang Jiang , Zhenjie Qi
A novel Cu(OAc)2-catalyzed tandem cyclization/addition strategy has been developed for the synthesis of pyrazoline substituted oxime ethers from β,γ-unsaturated hydrazones and oximes using K2S2O8 as an oxidant and NaHCO3 as a base has been achieved. The reaction demonstrates broad substrate scope, tolerating aryl, heteroaryl, alkyl, and sulfonyl substituents on both hydrazones and oximes, and provides the products in up to 78 % yield. Mechanistic studies suggest the involvement of both energy transfer and single electron transfer processes in accomplishing the radical 5-exo-trig cyclization to the CN bond. Furthermore, scale-up experiment was also enabled.
{"title":"Cu(OAc)2/K2S2O8 promoted aminooximation of β,γ-unsaturated hydrazones to access pyrazoline substituted oxime ethers","authors":"Quanlin Wu , Can Yang , Xinying Man , Xin Li , Quansen Wu , Yijing Zhang , Dongfang Jiang , Zhenjie Qi","doi":"10.1016/j.tet.2025.135036","DOIUrl":"10.1016/j.tet.2025.135036","url":null,"abstract":"<div><div>A novel Cu(OAc)<sub>2</sub>-catalyzed tandem cyclization/addition strategy has been developed for the synthesis of pyrazoline substituted oxime ethers from <em>β</em>,<em>γ</em>-unsaturated hydrazones and oximes using K<sub>2</sub>S<sub>2</sub>O<sub>8</sub> as an oxidant and NaHCO<sub>3</sub> as a base has been achieved. The reaction demonstrates broad substrate scope, tolerating aryl, heteroaryl, alkyl, and sulfonyl substituents on both hydrazones and oximes, and provides the products in up to 78 % yield. Mechanistic studies suggest the involvement of both energy transfer and single electron transfer processes in accomplishing the radical 5-<em>exo</em>-trig cyclization to the C<img>N bond. Furthermore, scale-up experiment was also enabled.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"190 ","pages":"Article 135036"},"PeriodicalIF":2.2,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145475158","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}
Palladium-catalyzed asymmetric arylation of α-2-nitrophenylsulfenylimino acetamide has been developed for the synthesis of arylglycine-containing peptides. The addition of a weakly coordinating anion is essential for the progress of this reaction. The protecting group of the arylated product is readily removed, and the resulting free amine undergoes N-terminal extension without racemization.
{"title":"Palladium-catalyzed asymmetric arylation of α-2-nitrophenylsulfenylimino acetamide","authors":"Tsubasa Inokuma , Koki Fukuhara , Masayuki Sugano , Maki Miyamoto , Takatoshi Someno , Ken-ichi Yamada","doi":"10.1016/j.tet.2025.135041","DOIUrl":"10.1016/j.tet.2025.135041","url":null,"abstract":"<div><div>Palladium-catalyzed asymmetric arylation of α-2-nitrophenylsulfenylimino acetamide has been developed for the synthesis of arylglycine-containing peptides. The addition of a weakly coordinating anion is essential for the progress of this reaction. The protecting group of the arylated product is readily removed, and the resulting free amine undergoes N-terminal extension without racemization.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"190 ","pages":"Article 135041"},"PeriodicalIF":2.2,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145526713","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 : 2026-01-15Epub Date: 2025-10-31DOI: 10.1016/j.tet.2025.135037
Feifei Wen , Xuyang Zhao , Xueqin Song , Huan Ma , Chengwang Wang , Yu Zhang , Pan Xie
A novel synergistic photoredox/palladium catalytic system has been developed for the visible light-induced decarboxylative benzoylation of arylpyridines using α-oxocarboxylic acids. This method proceeds efficiently at ambient temperature under aerobic conditions, employing Eosin Y as the photocatalyst, a Pd(II) complex as the transition metal catalyst, and K2S2O8 as the oxidant. A broad substrate scope, encompassing electron-donating and electron-withdrawing groups as well as diverse heterocyclic acids, afforded the corresponding benzoyl-substituted heteroarenes in moderate to good yields. This protocol offers an economical, mild, and sustainable strategy for the synthesis of valuable aromatic ketones, thereby advancing the field of dual photoredox/palladium catalysis.
{"title":"Visible light-induced synergistic photoredox/palladium catalysis for decarboxylative benzoylation of aryl pyridines: Efficient access to pyridine-substituted aryl ketones at ambient temperature","authors":"Feifei Wen , Xuyang Zhao , Xueqin Song , Huan Ma , Chengwang Wang , Yu Zhang , Pan Xie","doi":"10.1016/j.tet.2025.135037","DOIUrl":"10.1016/j.tet.2025.135037","url":null,"abstract":"<div><div>A novel synergistic photoredox/palladium catalytic system has been developed for the visible light-induced decarboxylative benzoylation of arylpyridines using <em>α</em>-oxocarboxylic acids. This method proceeds efficiently at ambient temperature under aerobic conditions, employing Eosin Y as the photocatalyst, a Pd(II) complex as the transition metal catalyst, and K<sub>2</sub>S<sub>2</sub>O<sub>8</sub> as the oxidant. A broad substrate scope, encompassing electron-donating and electron-withdrawing groups as well as diverse heterocyclic acids, afforded the corresponding benzoyl-substituted heteroarenes in moderate to good yields. This protocol offers an economical, mild, and sustainable strategy for the synthesis of valuable aromatic ketones, thereby advancing the field of dual photoredox/palladium catalysis.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"190 ","pages":"Article 135037"},"PeriodicalIF":2.2,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145475098","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 : 2026-01-15Epub Date: 2025-10-30DOI: 10.1016/j.tet.2025.135033
Musarrat Fatma, Faiz Ahmed Khan
Herein, we present an intramolecular palladium catalyzed cascade electrochemical reaction in an undivided cell at room temperature to afford benzoazepine-tethered acrylate derivatives. The reaction pathway is proposed to occur initially via selective iodination followed by 7-endo-dig selective cyclization followed by Heck coupling at room temperature using palladium catalyst. The reaction features broad substrate scope with good yields under mild condition and effectively underlines the role of expanding palladium assisted electrochemical transformation.
{"title":"Electrochemically driven benzoazepine-tethered acrylate synthesis","authors":"Musarrat Fatma, Faiz Ahmed Khan","doi":"10.1016/j.tet.2025.135033","DOIUrl":"10.1016/j.tet.2025.135033","url":null,"abstract":"<div><div>Herein, we present an intramolecular palladium catalyzed cascade electrochemical reaction in an undivided cell at room temperature to afford benzoazepine-tethered acrylate derivatives. The reaction pathway is proposed to occur initially <em>via</em> selective iodination followed by 7-<em>endo-</em>dig selective cyclization followed by Heck coupling at room temperature using palladium catalyst. The reaction features broad substrate scope with good yields under mild condition and effectively underlines the role of expanding palladium assisted electrochemical transformation.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"190 ","pages":"Article 135033"},"PeriodicalIF":2.2,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145415048","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 : 2026-01-15Epub Date: 2025-11-01DOI: 10.1016/j.tet.2025.135038
B. Berezhnoi, E. Chernoburova, I. Zavarzin, Y. Volkova
Naphthoxazole is a polycyclic heteroaromatic scaffold commonly found in bioactive molecules and natural products. However, effective and straightforward approaches to 2-amino substituted naphthoxazole remain challenging. We report here base-promoted cyclization of 1-nitroso-2-naphthol with isothiocyanates as a novel strategy for construction of 2-amino-substituted naphtho[1,2-d][1,3]oxazoles. The described method features short reaction time, the ability to scale up to gram-scale, good functional group tolerance, and readily available starting materials.
{"title":"Construction of 2-naphtho[1,2-d][1,3]oxazoles via base-promoted reaction of 1-nitroso-2-naphthol with isothiocyanates","authors":"B. Berezhnoi, E. Chernoburova, I. Zavarzin, Y. Volkova","doi":"10.1016/j.tet.2025.135038","DOIUrl":"10.1016/j.tet.2025.135038","url":null,"abstract":"<div><div>Naphthoxazole is a polycyclic heteroaromatic scaffold commonly found in bioactive molecules and natural products. However, effective and straightforward approaches to 2-amino substituted naphthoxazole remain challenging. We report here base-promoted cyclization of 1-nitroso-2-naphthol with isothiocyanates as a novel strategy for construction of 2-amino-substituted naphtho[1,2-<em>d</em>][1,3]oxazoles. The described method features short reaction time, the ability to scale up to gram-scale, good functional group tolerance, and readily available starting materials.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"190 ","pages":"Article 135038"},"PeriodicalIF":2.2,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145577161","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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