Tetrahedron chemPub Date : 2024-04-16DOI: 10.1016/j.tchem.2024.100073
Viktor Klöpfer , Anurag Chinchole , Oliver Reiser
{"title":"Dual iron- and organophotocatalyzed hydroformylation, hydroacylation and hydrocarboxylation of Michael-acceptors utilizing 1,3,5-trioxanes as C1-Synthone","authors":"Viktor Klöpfer , Anurag Chinchole , Oliver Reiser","doi":"10.1016/j.tchem.2024.100073","DOIUrl":"https://doi.org/10.1016/j.tchem.2024.100073","url":null,"abstract":"<div><p>A protocol based on photocatalytic cycles of both iron(III)chloride and 9,10-dicyanoanthracene (DCA) is developed for the masked hydroformylation, hydroacylation, and hydrocarboxylation of Michael-Acceptors utilizing readily available 1,3,5-trioxanes. Initiated by the LMCT of [FeCl<sub>4</sub>]<sup>–</sup> to generate chlorine radicals that promote hydrogen atom transfer (HAT) from the trioxanes, 9,10-dicyanoanthracene is used as co-photocatalyst to accelerate the formation of the desired products by facilitating the reoxidation of iron(II) to iron(III). The methodology is robust, allowing the generation of aldehydes, ketones, and carboxylic acids either by altering the trioxane and deprotection strategy or by subsequent photocatalyzed conversion of the initially obtained aldehydes.</p></div>","PeriodicalId":74918,"journal":{"name":"Tetrahedron chem","volume":"10 ","pages":"Article 100073"},"PeriodicalIF":0.0,"publicationDate":"2024-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2666951X24000123/pdfft?md5=6c9aa4e457cd19c96e477addafae25df&pid=1-s2.0-S2666951X24000123-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140644658","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tetrahedron chemPub Date : 2024-03-01DOI: 10.1016/j.tchem.2024.100070
Qian-Qian Hu , Jie Chen , Yang Yang , Hui Yang , Ling Zhou
{"title":"Strain-release transformations of bicyclo[1.1.0]butanes and [1.1.1]propellanes","authors":"Qian-Qian Hu , Jie Chen , Yang Yang , Hui Yang , Ling Zhou","doi":"10.1016/j.tchem.2024.100070","DOIUrl":"https://doi.org/10.1016/j.tchem.2024.100070","url":null,"abstract":"<div><p>Bicyclo[1.1.0]butanes (BCBs) and [1.1.1]propellanes (tricyclo[1.1.1.0<sup>1,3</sup>]pentanes, TCPs) are structurally unique compounds with different chemical properties. Strain-release driven reactions have emerged as an atom- and step-economic strategy for the organic synthesis. Using this strategy, a variety of functional ring molecules have been efficiently synthesized, including various cyclobutane molecules, bicyclo[2.1.1]hexanes, bicyclo[1.1.1]pentanes, and others. More specifically, these strain release-driven reactions include aspects of nucleophilic addition, radical addition, electrophilic or transition metal catalysis. This review will discuss the recent developments in the strain-release transformations of bicyclo[1.1.0]butanes and [1.1.1]propellanes.</p></div>","PeriodicalId":74918,"journal":{"name":"Tetrahedron chem","volume":"9 ","pages":"Article 100070"},"PeriodicalIF":0.0,"publicationDate":"2024-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2666951X24000093/pdfft?md5=0fe1d49a839e529aa565a8430072be9e&pid=1-s2.0-S2666951X24000093-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140016179","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tetrahedron chemPub Date : 2024-03-01DOI: 10.1016/j.tchem.2024.100068
Anrong Chen , Guoqiang Cheng , Feng Zhu
{"title":"Recent advances in stereoselective synthesis of non-classical glycosides","authors":"Anrong Chen , Guoqiang Cheng , Feng Zhu","doi":"10.1016/j.tchem.2024.100068","DOIUrl":"https://doi.org/10.1016/j.tchem.2024.100068","url":null,"abstract":"<div><p>Currently, glycosylation reactions predominantly target classical anomeric positions, with limited exploration of glycosylation at non-classical positions. However, there is ample reason to believe that this area is evolving into the next focal point and hotspot in glycosylation research. Therefore, summarizing and prospecting glycosylation reactions at non-classical positions over the past 5 years is deemed essential. This Minireview provides an overview of these transformations, emphasizing the reaction models and synthetic applications. We hope to stimulate future research to address the unmet synthetic challenges for the discovery of new non-classical glycosides, as well as to enhance the efficiency and overcome limitations of existing methods, especially in the construction of predictable and controllable stereoselective glycosides. By offering a comprehensive overview of the progress, our goal is to inspire further research and innovation in this exciting field.</p></div>","PeriodicalId":74918,"journal":{"name":"Tetrahedron chem","volume":"9 ","pages":"Article 100068"},"PeriodicalIF":0.0,"publicationDate":"2024-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2666951X2400007X/pdfft?md5=dfe71b357fcc6db15f489e0469c12b3e&pid=1-s2.0-S2666951X2400007X-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139992911","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Coordination-driven self-assembly formation of Ru(II)-metallocycles based on 4-amino-1,8-naphthalimide Tröger's base supramolecular scaffold: Synthesis, characterization, and heparin-binding study","authors":"Binduja Mohan, Ananthu Shanmughan, Mannanthara Kunhumon Noushija, Dipanjana Sarkar, Purti Patel, Sankarasekaran Shanmugaraju","doi":"10.1016/j.tchem.2024.100071","DOIUrl":"https://doi.org/10.1016/j.tchem.2024.100071","url":null,"abstract":"<div><p>The synthesis, characterization, and heparin polyanion sensing properties of a series of [2 + 2] self-assembled Ru(II)-metallocycles based on a green emitting 4-amino-1,8-naphthalimide Tröger's base (<strong>TBNap</strong>) supramolecular scaffold are described here. <strong>TBNap</strong> was reacted in a 2:2 stoichiometric ratio with a series of half-sandwiched Ru<sub>2</sub>(II)-acceptors (<strong>M</strong><sub><strong>1</strong></sub> to <strong>M</strong><sub><strong>4</strong></sub>) to isolate four new tetranuclear Ru(II)-metallocycles, <strong>TB-MC-1</strong> to <strong>TB-MC-4</strong>. All the metallocycles were characterized using NMR (<sup>1</sup>H & <sup>13</sup>C), FT-IR, and ESI-MS. A positive solvatochromism was observed for the metallocycles in different solvents with varying polarity. The strong-fluorescence emission of metallocycles was drastically quenched upon the addition of increasing concentration of heparin polyanions and the Stern-Volmer quenching constants (<em>K</em><sub>SV</sub>) were determined to be in the order of 10<sup>5</sup> M<sup>−1</sup>. All these results demonstrate the usefulness of metallocycles for sensing and quantifying the concentration of heparin polyanion.</p></div>","PeriodicalId":74918,"journal":{"name":"Tetrahedron chem","volume":"9 ","pages":"Article 100071"},"PeriodicalIF":0.0,"publicationDate":"2024-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2666951X2400010X/pdfft?md5=8ef1cec9f54116af8d46d62a45b2a032&pid=1-s2.0-S2666951X2400010X-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140062781","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tetrahedron chemPub Date : 2024-03-01DOI: 10.1016/j.tchem.2024.100069
Yu Huang, Ruizhi Yang, Wenbo H. Liu
{"title":"Recent advances of the Grignard-type reactions without involving organohalides","authors":"Yu Huang, Ruizhi Yang, Wenbo H. Liu","doi":"10.1016/j.tchem.2024.100069","DOIUrl":"https://doi.org/10.1016/j.tchem.2024.100069","url":null,"abstract":"<div><p>The Grignard-type reaction is a fundamentally important method for constructing C–C bonds in organic synthesis. The Grignard reagents are usually prepared through the metalation of organohalides. However, organohalides are mostly synthesized via corrosive halogenation reagents, which raises significant environmental concerns and increases the overall cost for the waste disposal. Consequently, it is essential to investigate alternative non-organohalide functionalities to access the Grignard-type reactivity. In this mini-review, we have summarized recent approaches to generating carbanions (or the equivalents) from carboxylic acids, ketones, aldehydes, olefins, and amines.</p></div>","PeriodicalId":74918,"journal":{"name":"Tetrahedron chem","volume":"9 ","pages":"Article 100069"},"PeriodicalIF":0.0,"publicationDate":"2024-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2666951X24000081/pdfft?md5=6a6fbdc85c80f61355917d89e233cba6&pid=1-s2.0-S2666951X24000081-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139993018","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tetrahedron chemPub Date : 2024-03-01DOI: 10.1016/j.tchem.2024.100067
Guizhou Yue , Bo Liu
{"title":"The photoinduced electron transfer (PET) reactions of silyl ethers and their application","authors":"Guizhou Yue , Bo Liu","doi":"10.1016/j.tchem.2024.100067","DOIUrl":"https://doi.org/10.1016/j.tchem.2024.100067","url":null,"abstract":"<div><p>Photocatalyzed organic reaction has been greatly developed and applied at the last 20 years, because photochemical synthesis is an efficiently green synthetic strategy, featuring simple operation, high chemical selectivity and low price <em>etc</em>. Meanwhile, organosilicon reagents have been widely used and developed in the field of organic synthesis since they were discovered. Photocatalyzed reactions of organosilicon compounds, especially silyl ethers, have taken advantages of mild condition, good selectivity and atom economy and been performed in synthesizing silicon-containing molecules and carbon skeleton molecules which were difficultly acquired by the traditional approaches. This review mainly introduced the reaction of silyl enol ethers, cyclopropyl silyl ethers, silyl acetals, silyl ethers and ketene silyl acetals via PET triggered by sensitizers/co-sensitizers, photocatalysts, electron donor-acceptor (EDA) complex, no photocatalysts and sensitizers and so on.</p></div>","PeriodicalId":74918,"journal":{"name":"Tetrahedron chem","volume":"9 ","pages":"Article 100067"},"PeriodicalIF":0.0,"publicationDate":"2024-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2666951X24000068/pdfft?md5=128202f5a0a2eab6a3bfa5ac519f3464&pid=1-s2.0-S2666951X24000068-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139993019","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Supramolecular hydrogelation triggered by a gold catalyst","authors":"Tomoya Yamamoto , Akiko Nakamura , Akari Mukaimine , Katsunori Tanaka","doi":"10.1016/j.tchem.2023.100058","DOIUrl":"10.1016/j.tchem.2023.100058","url":null,"abstract":"<div><p>Supramolecular gels formed by self-assembly of low-molecular-weight gelators have been attracting attention as biomaterials. In particular, various triggers for supramolecular hydrogelation, such as enzymatic reactions, have been developed to selectively induce the formation of gels at targeted sites <em>in vivo</em>. However, there are still limitations to the methods for triggering self-assembly, such as the selectivity of hydrogelation at targeted sites. Here, we report the first example of a low-molecular-weight hydrogelator whose gelation is triggered by catalytic amount of transition-metal complexes. This gelator consists of a substrate structure for a ring-closing reaction catalyzed by gold, and this reaction transforms the morphology of fibrils to induce hydrogelation in the presence of peptide additives. This novel trigger for hydrogelation will expand the applicability of a low-molecular-weight gelator <em>in vivo</em> when used with biocompatible metal catalysts.</p></div>","PeriodicalId":74918,"journal":{"name":"Tetrahedron chem","volume":"9 ","pages":"Article 100058"},"PeriodicalIF":0.0,"publicationDate":"2024-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2666951X23000244/pdfft?md5=6872d804de8e5cf9bc4845ce5bf65596&pid=1-s2.0-S2666951X23000244-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139015358","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tetrahedron chemPub Date : 2024-02-22DOI: 10.1016/j.tchem.2024.100064
Luis R. Domingo , Patricia Pérez , Mar Ríos-Gutiérrez , M. José Aurell
{"title":"A molecular electron density theory study of hydrogen bond catalysed polar Diels–Alder reactions of α,β-unsaturated carbonyl compounds","authors":"Luis R. Domingo , Patricia Pérez , Mar Ríos-Gutiérrez , M. José Aurell","doi":"10.1016/j.tchem.2024.100064","DOIUrl":"https://doi.org/10.1016/j.tchem.2024.100064","url":null,"abstract":"<div><p>The hydrogen bond (HB) catalysed Diels-Alder (DA) reactions of acrolein with cyclopentadiene have been investigated within the Molecular Electron Density Theory (MEDT) at the <em>ω</em>B97X-D/6-311G(d,p) computational level. The formation of HBs increases the electrophilicity of these species, suggesting an acceleration of these polar Diels-Alder (P-DA) reactions with forward electron density flux. Formation of one or two HBs with acrolein decreases the activation energies of the HB-catalysed P-DA reactions by 1.7 (methanol) and 4.0 (squaramide) kcal·mol<sup>−1</sup>, with the corresponding DA reactions exhibiting low <em>endo</em> stereoselectivity. These HB-catalysed DA reactions proceed through non-concerted one-step mechanisms via asynchronous transition state structures (TSs). An Interacting Quantum Atoms (IQA) energy partitioning analysis of the TSs indicates that the intra-atomic stabilization of the acrolein framework, coupled with the increase of the global electron density transfer, plays a crucial role in reducing the activation energies of these HB-catalysed DA reactions.</p></div>","PeriodicalId":74918,"journal":{"name":"Tetrahedron chem","volume":"10 ","pages":"Article 100064"},"PeriodicalIF":0.0,"publicationDate":"2024-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2666951X24000032/pdfft?md5=3c45e65bcb0a8c68ae6311981e65b963&pid=1-s2.0-S2666951X24000032-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140290639","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tetrahedron chemPub Date : 2024-02-18DOI: 10.1016/j.tchem.2024.100065
Ibrahim-Ethem Celik , Fabia Mittendorf , Adrián Gómez-Suárez, Stefan F. Kirsch
{"title":"Formal synthesis of bastimolide A using a chiral Horner-Wittig reagent and a bifunctional aldehyde as key building blocks","authors":"Ibrahim-Ethem Celik , Fabia Mittendorf , Adrián Gómez-Suárez, Stefan F. Kirsch","doi":"10.1016/j.tchem.2024.100065","DOIUrl":"10.1016/j.tchem.2024.100065","url":null,"abstract":"<div><p>The macrolide bastimolide A represents an attractive synthetic target due to its promising activity against resistant strains of the malaria pathogen plasmodium falciparum. We report a straightforward formal synthesis of bastimolide A using a Horner-Wittig reagent and an aldehyde derived from the same chiral-pool based intermediate as key building blocks.</p></div>","PeriodicalId":74918,"journal":{"name":"Tetrahedron chem","volume":"9 ","pages":"Article 100065"},"PeriodicalIF":0.0,"publicationDate":"2024-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2666951X24000044/pdfft?md5=1bfdfeaf3a5de169d18058869fa57347&pid=1-s2.0-S2666951X24000044-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139965564","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tetrahedron chemPub Date : 2024-02-17DOI: 10.1016/j.tchem.2024.100066
Showkat Rashid , Waseem I. Lone , Auqib Rashid , Bilal A. Bhat
{"title":"Inverse electron demand Diels-Alder reaction in total synthesis of bioactive natural products","authors":"Showkat Rashid , Waseem I. Lone , Auqib Rashid , Bilal A. Bhat","doi":"10.1016/j.tchem.2024.100066","DOIUrl":"https://doi.org/10.1016/j.tchem.2024.100066","url":null,"abstract":"<div><p>Among the various chemical reactions implemented during the total syntheses, the Inverse Electron Demand Diels-Alder Reaction <strong>(</strong>IEDDAR<strong>)</strong> is one of the crucial transformations utilized in building the complexity of bioactive natural products and drug-like molecules. Keeping in view the growing interest in harnessing the potential of this reaction, an overview of natural products that have been assembled through IEDDAR in the last 13 years (2011–2023) is presented through a selection of around 30 natural product total syntheses. In each case, the synthesis is presented schematically and the crucial IEDDAR step is duly highlighted in color. Additionally, wherever necessary, key structural features, characterization, biogenesis and biological activity attributes of the bioactive natural products are also discussed.</p></div>","PeriodicalId":74918,"journal":{"name":"Tetrahedron chem","volume":"9 ","pages":"Article 100066"},"PeriodicalIF":0.0,"publicationDate":"2024-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2666951X24000056/pdfft?md5=c0986ea237d2b130b8e461da9e14d2e0&pid=1-s2.0-S2666951X24000056-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139941680","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}