Pub Date : 2025-02-20DOI: 10.1016/j.tetlet.2025.155472
Xin Jin , Yong An , Jia Chen , Xianheng Wang , Huabin Wang , Changkuo Zhao , Qiang Huang
A vicinal diphosphorylation of enaminones with diaryl phosphine oxides have been established condition through AlCl3 as Lewis acid in this work. The transformation features excellent functional group tolerance, operational simplicity, and high yields, which provides an alternative strategy for accessing various diphosphoryl products 3a. Preliminary mechanism studies suggest the conversion between 1a and 2a involves the elimination of dimethylamine and cascade vicinal addition. This research provides significant value to the vicinal functionalization of enaminones.
{"title":"Vicinal diphosphorylation of enaminones with diaryl phosphine oxides via AlCl3-mediated CN bond cleavage","authors":"Xin Jin , Yong An , Jia Chen , Xianheng Wang , Huabin Wang , Changkuo Zhao , Qiang Huang","doi":"10.1016/j.tetlet.2025.155472","DOIUrl":"10.1016/j.tetlet.2025.155472","url":null,"abstract":"<div><div>A vicinal diphosphorylation of enaminones with diaryl phosphine oxides have been established condition through AlCl<sub>3</sub> as Lewis acid in this work. The transformation features excellent functional group tolerance, operational simplicity, and high yields, which provides an alternative strategy for accessing various diphosphoryl products <strong>3a</strong>. Preliminary mechanism studies suggest the conversion between <strong>1a</strong> and <strong>2a</strong> involves the elimination of dimethylamine and cascade vicinal addition. This research provides significant value to the vicinal functionalization of enaminones.</div></div>","PeriodicalId":438,"journal":{"name":"Tetrahedron Letters","volume":"158 ","pages":"Article 155472"},"PeriodicalIF":1.5,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143445859","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-18DOI: 10.1016/j.tetlet.2025.155509
Rozita Yazzaf , Mohammad Hosein Sayahi , Mohammad Mahdavi
A novel, metal-free strategy has been developed for the efficient synthesis of unique azetidine derivatives via a post-Ugi cyclization. This method involves generating 4-component Ugi adducts by reacting aldehydes, isocyanides, primary propargylamine, and 2-(phenylamino) benzoic acid. In the subsequent post-Ugi cyclization, azetidine derivatives are synthesized through a nucleophilic attack of a carbanion on the alkyne, followed by an intramolecular cyclization that forms a new carbon‑carbon bond.
{"title":"Post-Ugi cyclization approach for transition metal-free synthesis of Azetidine derivatives","authors":"Rozita Yazzaf , Mohammad Hosein Sayahi , Mohammad Mahdavi","doi":"10.1016/j.tetlet.2025.155509","DOIUrl":"10.1016/j.tetlet.2025.155509","url":null,"abstract":"<div><div>A novel, metal-free strategy has been developed for the efficient synthesis of unique azetidine derivatives via a post-Ugi cyclization. This method involves generating 4-component Ugi adducts by reacting aldehydes, isocyanides, primary propargylamine, and 2-(phenylamino) benzoic acid. In the subsequent post-Ugi cyclization, azetidine derivatives are synthesized through a nucleophilic attack of a carbanion on the alkyne, followed by an intramolecular cyclization that forms a new carbon‑carbon bond.</div></div>","PeriodicalId":438,"journal":{"name":"Tetrahedron Letters","volume":"158 ","pages":"Article 155509"},"PeriodicalIF":1.5,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143437737","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In oxindole alkaloids, stereoisomer formation occurs via bond cleavage at the spiro carbon center, followed by an intramolecular Mannich reaction. Since the possible common transition state possesses two prochiral faces, four stereoisomers at the C-3 and C-7 positions are potentially generated; however, few have been reported in nature. In this study, the four corynoxine stereoisomers were isolated, and their structures were elucidated. Two of these stereoisomers were found to be structurally unstable. Addtion of tartaric acid as a chemical trap reagent stabilized these isomers named corynoxines C and D and revealed their stereochemistries as 3R, 7S and 3R, 7R, respectively.
{"title":"Stabilization and structure elucidation of unstable Corynoxine-type stereoisomers using tartaric acid","authors":"Yuta Koseki , Ryosuke Sugiyama , Soichiro Nishimura , Takako Sugahara , Ryuji Asano , Mami Yamazaki , Katsuyuki Aoki","doi":"10.1016/j.tetlet.2025.155510","DOIUrl":"10.1016/j.tetlet.2025.155510","url":null,"abstract":"<div><div>In oxindole alkaloids, stereoisomer formation occurs via bond cleavage at the spiro carbon center, followed by an intramolecular Mannich reaction. Since the possible common transition state possesses two prochiral faces, four stereoisomers at the C-3 and C-7 positions are potentially generated; however, few have been reported in nature. In this study, the four corynoxine stereoisomers were isolated, and their structures were elucidated. Two of these stereoisomers were found to be structurally unstable. Addtion of tartaric acid as a chemical trap reagent stabilized these isomers named corynoxines C and D and revealed their stereochemistries as 3<em>R</em>, 7<em>S</em> and 3<em>R</em>, 7<em>R</em>, respectively.</div></div>","PeriodicalId":438,"journal":{"name":"Tetrahedron Letters","volume":"158 ","pages":"Article 155510"},"PeriodicalIF":1.5,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143437736","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-16DOI: 10.1016/j.tetlet.2025.155505
Chen Wang , Zhihua Wang , Jinliang Zhang , Miaomiao Mu , Jin Zhang , Zhiming Wang , Jianguo Yang , Guobo Huang , Xiaolei Zhu
A visible-light promoted radical coupling of difluoroenol silyl ethers and difluorinated Pyf-sulfides has been developed. This protocol provides a simple and straightforward approach to assemble diverse functionalized tetrafluoroethylene-containing compounds in moderate to good yields.
{"title":"Visible-light promoted radical coupling of difluoroenol silyl ethers and difluorinated Pyf-sulfides to construct tetrafluoroethylene-containing compounds","authors":"Chen Wang , Zhihua Wang , Jinliang Zhang , Miaomiao Mu , Jin Zhang , Zhiming Wang , Jianguo Yang , Guobo Huang , Xiaolei Zhu","doi":"10.1016/j.tetlet.2025.155505","DOIUrl":"10.1016/j.tetlet.2025.155505","url":null,"abstract":"<div><div>A visible-light promoted radical coupling of difluoroenol silyl ethers and difluorinated Pyf-sulfides has been developed. This protocol provides a simple and straightforward approach to assemble diverse functionalized tetrafluoroethylene-containing compounds in moderate to good yields.</div></div>","PeriodicalId":438,"journal":{"name":"Tetrahedron Letters","volume":"158 ","pages":"Article 155505"},"PeriodicalIF":1.5,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143511826","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Collagen, a fibrous protein, accounts for 30 % of all proteins in the human body and serves as an essential extracellular matrix component that imparts mechanical strength to connective tissues such as skin and bones. Deoxypyridinoline, a collagen crosslinking amino acid, was first isolated from bovine bone in 1982. This compound is released into the bloodstream during bone resorption without being reused and has recently garnered attention as a biomarker for osteoporosis. In this study, we achieved the total synthesis of deoxypyridinoline, with a 22 % overall yield, in five steps from commercially available protected amino acids. The synthesis would aid a quantitative analysis of deoxypyridinoline as an alternative to isolating it from natural sources.
{"title":"Total synthesis of collagen crosslinker deoxypyridinoline","authors":"Hiroaki Ishii, Ryosuke Shigeta, Kaho Oishi, Toyonobu Usuki","doi":"10.1016/j.tetlet.2025.155508","DOIUrl":"10.1016/j.tetlet.2025.155508","url":null,"abstract":"<div><div>Collagen, a fibrous protein, accounts for 30 % of all proteins in the human body and serves as an essential extracellular matrix component that imparts mechanical strength to connective tissues such as skin and bones. Deoxypyridinoline, a collagen crosslinking amino acid, was first isolated from bovine bone in 1982. This compound is released into the bloodstream during bone resorption without being reused and has recently garnered attention as a biomarker for osteoporosis. In this study, we achieved the total synthesis of deoxypyridinoline, with a 22 % overall yield, in five steps from commercially available protected amino acids. The synthesis would aid a quantitative analysis of deoxypyridinoline as an alternative to isolating it from natural sources.</div></div>","PeriodicalId":438,"journal":{"name":"Tetrahedron Letters","volume":"158 ","pages":"Article 155508"},"PeriodicalIF":1.5,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143511827","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-13DOI: 10.1016/j.tetlet.2025.155503
Yuxin Wang , Changkang Li , Songyang Sui, Jimei Liu, Jungui Dai
Mediataxanes A–C (1–3), three unusual 4-oxo-20-nor-taxanes with 6/8/6 ring system were isolated from Taxus × media cell cultures. Their structures were determined by extensive spectroscopic data, and the absolute configurations were confirmed by X-ray crystallographic analysis (1 and 2) and NMR data comparison (3). Biological assay revealed that 1 exhibited moderate cytotoxicity against gastric carcinoma BGC823 and cervical cancer HeLa cells. In addition, a plausible mechanism for the oxidative cleavage of 4(20)-exocyclic-double bond and the formation of 4-carbonyl group in 1–3 is proposed.
{"title":"Three unusual 4-oxo-20-nor-taxanes from the cell cultures of Taxus × media","authors":"Yuxin Wang , Changkang Li , Songyang Sui, Jimei Liu, Jungui Dai","doi":"10.1016/j.tetlet.2025.155503","DOIUrl":"10.1016/j.tetlet.2025.155503","url":null,"abstract":"<div><div>Mediataxanes A–C (<strong>1</strong>–<strong>3</strong>), three unusual 4-oxo-20-<em>nor</em>-taxanes with 6/8/6 ring system were isolated from <em>Taxus × media</em> cell cultures. Their structures were determined by extensive spectroscopic data, and the absolute configurations were confirmed by X-ray crystallographic analysis (<strong>1</strong> and <strong>2</strong>) and NMR data comparison (<strong>3</strong>). Biological assay revealed that <strong>1</strong> exhibited moderate cytotoxicity against gastric carcinoma BGC823 and cervical cancer HeLa cells. In addition, a plausible mechanism for the oxidative cleavage of 4(20)-exocyclic-double bond and the formation of 4-carbonyl group in <strong>1</strong>–<strong>3</strong> is proposed.</div></div>","PeriodicalId":438,"journal":{"name":"Tetrahedron Letters","volume":"158 ","pages":"Article 155503"},"PeriodicalIF":1.5,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143395967","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Herein we report an efficient and eco-friendly methodology for the selective synthesis of 1,2-bis-organylselanyl alkenes from diorganyl diselenides and terminal alkynes. In this regard, the use of the water extract of rice straw ash (WERSA) proved to be an efficient reaction media promoting the synthesis of the desired compounds in up to 97 % yield with reasonable stereoselectivity. Furthermore, the combination of experimental studies and DFT calculations enabled us to propose a plausible reaction pathway.
{"title":"A sustainable approach for the bis-selenylation of alkynes: Design, synthesis and mechanistic studies","authors":"Lucas Martins Correa Böhs , Calebe Hebrom Livistom Silva , Natália Emanuele Biolosor Kuntz , Benhur Godoi , Andrielli Leitemberger , Marcelo Godoi","doi":"10.1016/j.tetlet.2025.155504","DOIUrl":"10.1016/j.tetlet.2025.155504","url":null,"abstract":"<div><div>Herein we report an efficient and eco-friendly methodology for the selective synthesis of 1,2-<em>bis</em>-organylselanyl alkenes from diorganyl diselenides and terminal alkynes. In this regard, the use of the water extract of rice straw ash (<em>WERSA</em>) proved to be an efficient reaction media promoting the synthesis of the desired compounds in up to 97 % yield with reasonable stereoselectivity. Furthermore, the combination of experimental studies and DFT calculations enabled us to propose a plausible reaction pathway.</div></div>","PeriodicalId":438,"journal":{"name":"Tetrahedron Letters","volume":"158 ","pages":"Article 155504"},"PeriodicalIF":1.5,"publicationDate":"2025-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143420360","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-05DOI: 10.1016/j.tetlet.2025.155502
Xiaoke Luo , Yanmei Wen , Junjie Yang, Haisheng Xie
Palladium-catalyzed green oxidative homocoupling reactions of CvinylH bonds of terminal alkenes produce conjugated dienes by using O2 as the crucial oxidant. This method provides an efficient and environmentally compatible approach to 1,3-butadienes under mild conditions, addressing the need for more sustainable reaction processes. Our preliminary results demonstrate the viability of dehydrogenative CvinylCvinyl bond-forming processes with molecular oxygen as the sole oxidant, offering a promising strategy for green chemistry applications.
{"title":"Synthesis of conjugated dienes through dehydrgeogenative homocoupling reaction of vinyl CH substrates using oxygen as oxidant","authors":"Xiaoke Luo , Yanmei Wen , Junjie Yang, Haisheng Xie","doi":"10.1016/j.tetlet.2025.155502","DOIUrl":"10.1016/j.tetlet.2025.155502","url":null,"abstract":"<div><div>Palladium-catalyzed green oxidative homocoupling reactions of C<sub>vinyl</sub><img>H bonds of terminal alkenes produce conjugated dienes by using O<sub>2</sub> as the crucial oxidant. This method provides an efficient and environmentally compatible approach to 1,3-butadienes under mild conditions, addressing the need for more sustainable reaction processes. Our preliminary results demonstrate the viability of dehydrogenative C<sub>vinyl</sub><img>C<sub>vinyl</sub> bond-forming processes with molecular oxygen as the sole oxidant, offering a promising strategy for green chemistry applications.</div></div>","PeriodicalId":438,"journal":{"name":"Tetrahedron Letters","volume":"158 ","pages":"Article 155502"},"PeriodicalIF":1.5,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143395966","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-05DOI: 10.1016/j.tetlet.2025.155486
Zi-En Liu , Tao Lin , Yue Zhao, Jun Cao
A novel Pd(0)-catalyzed CH (phenylsulfonyl)difluoromethylation of electron-rich heteroarenes has been developed. The reaction utilizing PhSO2CF2I as a (phenylsulfonyl)difluoromethylation reagent proceeds efficiently. Mechanistic studies indicate that the CH (phenylsulfonyl)difluoromethylation occurs via a radical pathway. This method demonstrates broad substrate compatibility, including a variety of heterocycles containing nitrogen, oxygen, and sulfur atoms, achieving excellent yields. This study provides an efficient and versatile approach for synthesizing (phenylsulfonyl)difluoromethylated heterocycles, which are valuable in pharmaceuticals, agrochemicals, and materials. The mild reaction conditions and high efficiency of this method make it a promising tool for expanding the scope of organofluorine chemistry applications.
{"title":"Pd-catalyzed CH (phenylsulfonyl)difluoromethylation of electron-rich heteroarenes","authors":"Zi-En Liu , Tao Lin , Yue Zhao, Jun Cao","doi":"10.1016/j.tetlet.2025.155486","DOIUrl":"10.1016/j.tetlet.2025.155486","url":null,"abstract":"<div><div>A novel Pd(0)-catalyzed C<img>H (phenylsulfonyl)difluoromethylation of electron-rich heteroarenes has been developed. The reaction utilizing PhSO<sub>2</sub>CF<sub>2</sub>I as a (phenylsulfonyl)difluoromethylation reagent proceeds efficiently. Mechanistic studies indicate that the C<img>H (phenylsulfonyl)difluoromethylation occurs <em>via</em> a radical pathway. This method demonstrates broad substrate compatibility, including a variety of heterocycles containing nitrogen, oxygen, and sulfur atoms, achieving excellent yields. This study provides an efficient and versatile approach for synthesizing (phenylsulfonyl)difluoromethylated heterocycles, which are valuable in pharmaceuticals, agrochemicals, and materials. The mild reaction conditions and high efficiency of this method make it a promising tool for expanding the scope of organofluorine chemistry applications.</div></div>","PeriodicalId":438,"journal":{"name":"Tetrahedron Letters","volume":"158 ","pages":"Article 155486"},"PeriodicalIF":1.5,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143324810","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-04DOI: 10.1016/j.tetlet.2025.155492
Yunfei Liu, Kaikai Qiao, Junfeng Yang, Wenfeng Jiang, Rong Zhang, Lei Shi
We have established an MHAT-driven oxidation process to transform olefins into ketones, using inexpensive and readily available iron phthalocyanine as a catalyst. Various acetophenone derivatives were obtained with a low catalyst loading of only 0.5 mol% at room temperature and in an air atmosphere. This methodology has good compatibility with a wide range of differently substituted functional groups.
{"title":"Iron phthalocyanine-catalyzed aerobic oxidation of olefins enabled by metal-hydride hydrogen atom transfer","authors":"Yunfei Liu, Kaikai Qiao, Junfeng Yang, Wenfeng Jiang, Rong Zhang, Lei Shi","doi":"10.1016/j.tetlet.2025.155492","DOIUrl":"10.1016/j.tetlet.2025.155492","url":null,"abstract":"<div><div>We have established an MHAT-driven oxidation process to transform olefins into ketones, using inexpensive and readily available iron phthalocyanine as a catalyst. Various acetophenone derivatives were obtained with a low catalyst loading of only 0.5 mol% at room temperature and in an air atmosphere. This methodology has good compatibility with a wide range of differently substituted functional groups.</div></div>","PeriodicalId":438,"journal":{"name":"Tetrahedron Letters","volume":"158 ","pages":"Article 155492"},"PeriodicalIF":1.5,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143377443","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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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