Organic chemistry frontiers : an international journal of organic chemistry最新文献

Investigating the stereo-directing effect of remote participating groups on selectivity in the 2-deoxyglycosylation of galactal† 远距离参与基团对银河2-脱氧糖基化选择性的立体定向效应研究

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-03-11 DOI: 10.1039/d4qo02329c

Nitin Kumar , Ankit Yadav , Sudhir Kashyap

{"title":"Investigating the stereo-directing effect of remote participating groups on selectivity in the 2-deoxyglycosylation of galactal†","authors":"Nitin Kumar , Ankit Yadav , Sudhir Kashyap","doi":"10.1039/d4qo02329c","DOIUrl":"10.1039/d4qo02329c","url":null,"abstract":"<div><div>Chemical glycosylation is arguably crucial for assembling the structurally defined polysaccharides and glycoconjugates of distinctive biological functions. Predicting and governing the stereochemical outcome in the glycosylation reaction is undoubtedly more challenging and influenced mainly by the configuration of protecting groups (PGs) and ring conformers. In this paper, we exploited the direct influence of stereoelectronically diverse PGs on the anomeric selectivity in 2-deoxyglycosylation. The galactal donors with C-4 <em>O</em>-pivaloyl as a higher electron density group ensured enhanced α-selectivity; practically, trichloroacetimidate (<em>O</em>-TCA) ensured optimal selectivity, affirming the covalent remote group participation (RGP) featuring distinctive ring-bridging oxazepine structures. Mechanistic investigations employing density functional theory (DFT) and experimental studies revealed the perspective of RGP by distal C-4 PGs, which facilitate the stabilization of <sup><em>4</em></sup><em>H</em><sub><em>3</em></sub> and <sup><em>3</em></sup><em>H</em><sub><em>4</em></sub> conformations of oxocarbenium ions <em>via</em> dioxolenium species.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 11","pages":"Pages 3426-3437"},"PeriodicalIF":0.0,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143570338","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Mechanistic study on the enantiodivergent kinetic resolution of axial chiral binaphthol via the peptide-phosphonium salt-catalyzed Atherton–Todd reaction† 通过肽-鏻盐催化的阿瑟顿-托德反应对轴向手性二萘酚进行对映异构动力学解析的机理研究

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-03-11 DOI: 10.1039/d5qo00119f

Jiajia He , Xingjie Luo , Siqiang Fang , Zhishan Su , Changwei Hu , Tianli Wang

{"title":"Mechanistic study on the enantiodivergent kinetic resolution of axial chiral binaphthol via the peptide-phosphonium salt-catalyzed Atherton–Todd reaction†","authors":"Jiajia He , Xingjie Luo , Siqiang Fang , Zhishan Su , Changwei Hu , Tianli Wang","doi":"10.1039/d5qo00119f","DOIUrl":"10.1039/d5qo00119f","url":null,"abstract":"<div><div>Density functional theory calculations were conducted to elucidate the mechanism and stereoselectivity of the Atherton–Todd reaction-guided enantiodivergent kinetic resolution of axial chiral binaphthol catalyzed by peptide-phosphonium salts. The reaction involved the formation of two reactive phosphorus species: diphenylphosphinic chloride and diphenylphosphinic anhydride . Subsequent nucleophilic acylation of the deprotonated diol anion with / yielded chiral <em>O</em>-phosphorylation products. The hydrolysis of was identified as the rate-determining step in the uncatalyzed reaction. Peptide-phosphonium salts accelerated the hydrolysis of , reducing the energy barriers for the → transformation, for the two phosphonium salts with diverse side chains ( and ). In the kinetic resolution process, the chiral peptide-phosphonium salt catalysts simultaneously activated the diol anion and / through ion-pairing and multiple hydrogen bonding interactions. preferentially interacted with and the <em>R</em>-diol anion <em>via</em> favorable π–π stacking, affording the <em>R</em>-product, while exhibited higher affinity for and the <em>S</em>-diol anion due to significant steric effects, leading to the formation of the <em>S</em>-atropisomer. Structural analysis of five representative catalysts revealed that silicon substituents, steric effects from Bn and Boc groups, and dipeptide skeletons collectively contributed to a well-defined chiral environment. These features enhanced the catalyst's rigidity and chiral recognition ability, enabling excellent enantioselectivity.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 11","pages":"Pages 3389-3402"},"PeriodicalIF":0.0,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143589824","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Stabilized carbon radical-mediated three-component polyfluoroalkylation of amino acid derivatives† 稳定碳自由基介导的氨基酸衍生物的三组分多氟烷基化

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-03-11 DOI: 10.1039/d5qo00208g

Meizhong Tang , Ye Wang , Shenlin Huang , Lan-Gui Xie

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Switchable divergent organocatalytic asymmetric reactions of azlactones with 1,4-enediones† 唑内酯与1,4-烯二酮的可切换发散性有机催化不对称反应

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-03-11 DOI: 10.1039/d5qo00280j

Luyao Li , Dandan Pan , Gongming Zhu , Chenhe Su , Bo Zhu

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Single-atom editing for the construction of boron-containing heterocycles 构建含硼杂环的单原子编辑技术

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-03-11 DOI: 10.1039/d5qo00210a

Xue Li , Yi-Ming Chen , Zhi-Gang Xu

{"title":"Single-atom editing for the construction of boron-containing heterocycles","authors":"Xue Li , Yi-Ming Chen , Zhi-Gang Xu","doi":"10.1039/d5qo00210a","DOIUrl":"10.1039/d5qo00210a","url":null,"abstract":"<div><div>In recent years, there has been a significant surge in research on boron-containing pharmaceuticals, with particular emphasis on their anti-inflammatory and antibacterial properties, as well as their potential to inhibit tumor growth. The advent of single-atom editing technology, which facilitates rapid modifications to complex molecules, has markedly enhanced the efficiency and speed of pharmaceutical compound synthesis. This review aims to compile and evaluate the extant literature on the synthesis of boron heterocycles employing single-atom editing methodologies. The synthesis of these compounds predominantly entails the addition of atoms to pre-existing boron-containing heterocycles or the insertion of boron atoms into alternative heterocyclic frameworks. Although examples of such reactions are relatively scant and the research has yet to be fully systematized, presenting a somewhat fragmented appearance, the extant body of reactions is sufficiently robust to underscore the importance of these boron insertion processes, thereby attracting greater attention to this field and stimulating the interest of researchers.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 11","pages":"Pages 3521-3533"},"PeriodicalIF":0.0,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675178","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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Unveiling stereoselective ladders via photo-oligomerization of a diazaanthracene macrocycle† 通过光寡聚揭示重氮蒽大环的立体选择性阶梯

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-03-11 DOI: 10.1039/d5qo00159e

Jinti Moni Kumar , Ivan Huc , Yann Ferrand , Bappaditya Gole

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Electrochemical C(sp3)–S bond cleavage of thioethers: an approach for simultaneous utilization of carbon- and sulfur-fragments† 硫醚的电化学C(sp3) - s键裂解：同时利用碳和硫碎片的方法

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-03-11 DOI: 10.1039/d5qo00248f

Jiawei Huang , Xiaoman Li , Liang Xu , Yu Wei

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Electrochemical strategies for N-alkylation and N-acylation of NH-sulfoximines via the decarboxylation and deoxygenation of carboxylic acids† 羧酸脱羧和脱氧作用下nh -亚砜亚胺n -烷基化和n -酰化的电化学策略

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-03-11 DOI: 10.1039/d5qo00068h

Xiaoman Li , Jiawei Huang , Ji-Xing Zhao , Liang Xu , Ping Liu , Jichang Liu , Yu Wei

引用次数: 0

Strain-release driven α,β-difunctionalization of cyclopropanols with bromonaphthols† 菌株释放驱动环丙醇与溴萘酚的α， β-双官能化

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-03-11 DOI: 10.1039/d4qo02439g

Feng-Cheng Jia , Lei-Xiao Luo , Yao-Hui Chen , Qian Xiang , Xiao-Qiang Hu , Shuang-Xi Gu

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Dibenzo-12-crown-4 group as a pore-forming enhancer for anion transport† 二苯并-12-冠-4基团作为阴离子输运的成孔促进剂

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-03-11 DOI: 10.1039/d5qo00025d

Jisen Fan , Yingxue Xu , Jie Shen , Wenju Chang , Huaqiang Zeng

{"title":"Dibenzo-12-crown-4 group as a pore-forming enhancer for anion transport†","authors":"Jisen Fan , Yingxue Xu , Jie Shen , Wenju Chang , Huaqiang Zeng","doi":"10.1039/d5qo00025d","DOIUrl":"10.1039/d5qo00025d","url":null,"abstract":"<div><div>Dysregulation of anion transport is implicated in a range of diseases, including congenital myotonia, cystic fibrosis, and hereditary renal lithiasis. While natural anion channels exhibit highly complex and intricate structures, the development of structurally simpler artificial channels holds promise for advancing the understanding of anion transport mechanisms and offering novel therapeutic approaches. Among emerging strategies, the use of side chain–side chain interactions to construct artificial anion channels has shown significant potential, particularly through the application of flexible hydrocarbon side chains to facilitate pore formation. Building on this concept, we introduce a novel scaffold—the dibenzo-12-crown-4 group—which unexpectedly acts as a pore-forming enhancer, rather than a cation transporter. By strengthening side chain–side chain interactions, this group promotes the formation of sizable pores within lipid bilayers, selectively and efficiently transporting anions, rather than cations. Notably, channel exhibits a remarkable high Cl<sup>−</sup>/K<sup>+</sup> selectivity ratio of 17 while showcasing a distinct hierarchy in anion conductivity: ClO<sub>4</sub><sup>−</sup> > I<sup>−</sup> > NO<sub>3</sub><sup>−</sup> > Br<sup>−</sup> > Cl<sup>−</sup>.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 11","pages":"Pages 3409-3416"},"PeriodicalIF":0.0,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635461","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0