TetrahedronPub Date : 2025-03-25DOI: 10.1016/j.tet.2025.134616
Alberto Insuasty , Serena Carrara , Doan Vu , Joel José Montalvo-Acosta , Alejandro Ortíz , Conor Hogan , Christopher R. McNeill , Steven J. Langford
{"title":"Synthesis and evaluation of new isoquinoline diimide derivatives as small molecule acceptors for organic solar cells","authors":"Alberto Insuasty , Serena Carrara , Doan Vu , Joel José Montalvo-Acosta , Alejandro Ortíz , Conor Hogan , Christopher R. McNeill , Steven J. Langford","doi":"10.1016/j.tet.2025.134616","DOIUrl":"10.1016/j.tet.2025.134616","url":null,"abstract":"<div><div>In this work we explore the use of the method of oxidation and heterocyclization of naphthalene diimides (NDIs) to obtain five novel isoquinoline diimide derivatives (<strong>IQDI 3</strong>–<strong>7</strong>) as new small molecule acceptors. These derivatives comprise a main core based on triphenylamine (TPA) as electron-donor linked to an isoquinoline diimide moiety as a new electron-acceptor (<strong>IQDI 3</strong>). The effect on the electronic properties of a further functionalization on TPA achieving A-D-A architectures with additional electron acceptors moieties such as carbonyl group (<strong>IQDI 4</strong>), 3-methylrhodanine (<strong>IQDI 5</strong>), 1,3-indandione (<strong>IQDI 6</strong>) and malononitrile (<strong>IQDI 7</strong>) was studied. Their electrochemical and optoelectronic properties as well as their performance in photovoltaic devices using <strong>J52</strong> as electron-donor polymer were studied being <strong>IQDI 6</strong> the compound that showed the best PCE % value.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"178 ","pages":"Article 134616"},"PeriodicalIF":2.1,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143724278","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
TetrahedronPub Date : 2025-03-25DOI: 10.1016/j.tet.2025.134619
C. Elizabeth Adams, Steven D. Townsend
{"title":"Studies toward the synthesis of yaretol: an unexpected rearrangement en route to the tricyclic core","authors":"C. Elizabeth Adams, Steven D. Townsend","doi":"10.1016/j.tet.2025.134619","DOIUrl":"10.1016/j.tet.2025.134619","url":null,"abstract":"<div><div>Yaretol is a polycyclic norditerpene constituting a structurally distinct class of terpene natural products isolated from <em>Azorella madreporica</em> which, to date, has not been accessed via total synthesis. Herein, we report our synthetic efforts toward a key intramolecular Diels-Alder furan (IMDAF) cycloaddition to construct the carbon framework. We discuss our efforts toward the cycloaddition wherein undesired aromatization and unanticipated rearrangement of the cycloadduct are observed.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"178 ","pages":"Article 134619"},"PeriodicalIF":2.1,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143735117","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
TetrahedronPub Date : 2025-03-25DOI: 10.1016/j.tet.2025.134618
Xiao-Wei Cong , Yu Peng
{"title":"Synthesis of the ACDE tetracyclic skeleton in ceforalide B","authors":"Xiao-Wei Cong , Yu Peng","doi":"10.1016/j.tet.2025.134618","DOIUrl":"10.1016/j.tet.2025.134618","url":null,"abstract":"<div><div>Ceforalide B is a representative molecule with a complex rigid skeleton composed of ABCDE pentacycle in the benzenoid cephalotane-type norditerpenoids family, which contains five contiguous stereogenic centers involving an all-carbon quaternary center. An advanced intermediate with the ACDE rings has been synthesized from 3,5-dimethylphenol. While the organocatalyzed diastereoselective intramolecular Michael addition and aldol condensation reaction successfully secure the rapid construction of the ACD tricyclic framework, the Yb(OTf)<sub>3</sub>-catalyzed stereoselective hydroxymethylation, 1,2-addition, followed by a PDC-mediated oxidative rearrangement reaction also play important roles in elaborating this tricyclic core. Additionally, the late-stage C1 epimerization and the construction of bridging lactone for E ring by a Mitsunobu reaction were further used to build the tetracyclic carbon skeleton.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"179 ","pages":"Article 134618"},"PeriodicalIF":2.1,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143738020","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}
TetrahedronPub Date : 2025-03-25DOI: 10.1016/j.tet.2025.134620
Xiuyuan Duan, Guojun Zheng
{"title":"Visible-light-driven synthesis of benzoxepine derivatives from aromatic diazo compounds","authors":"Xiuyuan Duan, Guojun Zheng","doi":"10.1016/j.tet.2025.134620","DOIUrl":"10.1016/j.tet.2025.134620","url":null,"abstract":"<div><div>The most well-known reaction between diazo compounds and alkenes is cyclopropanation, which proceeds via a metal carbene or free carbene intermediate. In recent years, significant progress has been made in visible-light photocatalysis of diazo compounds to generate radicals and subsequent functionalization reactions. In this work, the photocatalytic intramolecular radical cyclization of aryl diazo compounds has been developed, resulting in the formation of benzoxepine derivatives with moderate yields. Mechanistic experiments support the formation of a carbon-centered radical from the diazoalkane via a proton-coupled electron transfer (PCET) process. This reaction, which is easy to perform, allowing the rapid conversion of aryl diazo compounds into benzoxepine derivatives under mild conditions.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"179 ","pages":"Article 134620"},"PeriodicalIF":2.1,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143748588","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}
TetrahedronPub Date : 2025-03-25DOI: 10.1016/j.tet.2025.134613
B.V. Subba Reddy
{"title":"Editorial for the special issue commemorating the 90th birthday of Dr A V Rama Rao","authors":"B.V. Subba Reddy","doi":"10.1016/j.tet.2025.134613","DOIUrl":"10.1016/j.tet.2025.134613","url":null,"abstract":"","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"178 ","pages":"Article 134613"},"PeriodicalIF":2.1,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758975","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}
TetrahedronPub Date : 2025-03-22DOI: 10.1016/j.tet.2025.134607
Zhong-Lian Ma , Zhi-Pu Yu , Ling Lv , Zhi-Qing Liu , Chang-Yun Wang , Guang-Shan Yao
{"title":"A new sesquiterpene with a specialized [4,4] bicyclononane skeleton from the marine-derived fungus Metarhizium sp. P2100","authors":"Zhong-Lian Ma , Zhi-Pu Yu , Ling Lv , Zhi-Qing Liu , Chang-Yun Wang , Guang-Shan Yao","doi":"10.1016/j.tet.2025.134607","DOIUrl":"10.1016/j.tet.2025.134607","url":null,"abstract":"<div><div>An oxidized 5/5/6 tricyclic sesquiterpene with a new 6-isopropyl-1,2,9-trimethyl-spiro [4.4]nonane carbon skeleton, metarhizane A (<strong>1</strong>), was isolated from a rare marine derived fungus <em>Metarhizium</em> sp. P2100. Its structure and the absolute configurations were assigned by interpretation of a combination of spectroscopic data and X-ray diffraction. This is the first example with a spiro [4,4] nonane core among the sesquiterpene skeletons. A plausible biosynthetic pathway for metarhizane A (<strong>1</strong>) initiated from farnesyl diphosphate (FPP) was predicted and discussed. The above results suggested that this marine-derived fungus has the potential to produce novel skeletons.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"178 ","pages":"Article 134607"},"PeriodicalIF":2.1,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143704603","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}
TetrahedronPub Date : 2025-03-22DOI: 10.1016/j.tet.2025.134611
Hiroto Kimura , Takuya Hashimoto
{"title":"Imidazole-mediated defluorosulfonylation of N-(fluorosulfonyl)oxazolidinones accessed by an organoiodine(I/III)-catalyzed oxyamination","authors":"Hiroto Kimura , Takuya Hashimoto","doi":"10.1016/j.tet.2025.134611","DOIUrl":"10.1016/j.tet.2025.134611","url":null,"abstract":"<div><div>Oxazolidinones are used as drug motifs and chiral auxiliaries in synthetic organic chemistry. We report herein an imidazole-mediated deprotection of N-(fluorosulfonyl)oxazolidinones to N-unprotected oxazolidinones. Given the accessibility of enantioenriched N-(fluorosulfonyl)oxazolidinones via our organoiodine-catalyzed enantioselective oxyamination of alkenes, this procedure offers a new and robust method to generate valuable oxazolidinone scaffolds.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"178 ","pages":"Article 134611"},"PeriodicalIF":2.1,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143725828","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}
{"title":"Stereoselective synthesis of novel 4′-methylsulfanyl-pyrimidine ribonucleosides by means of nucleophilic substitution of the 4′-benzoyloxy leaving group","authors":"Kazuhiro Haraguchi , Yasuaki Kimura , Hiroshi Abe , Hiroki Kumamoto , Hiromichi Tanaka","doi":"10.1016/j.tet.2025.134581","DOIUrl":"10.1016/j.tet.2025.134581","url":null,"abstract":"<div><div>A synthetic route for the novel nucleosides 4′-methylsulfanyluridine (<strong>20a</strong>) and –cytidine (<strong>26</strong>) has been developed. This route consists of two steps; 1) preparation of 4′-<em>O</em>-benzoyloxy-xylofuranosylnucleoside <strong>13</strong> through electrophilic iodo-benzoyloxylation to 4′,5′-unsaturated uracil nulesoside <strong>9</strong> and replacement of the iodo-substituent at the 5′-position with the benzoyloxy group, 2) nucleophilic substitution of <strong>13</strong> with Me<sub>3</sub>SiSMe leading to the 4′-α-methylsulfanylnucleoside <strong>14a</strong> stereoselectively. The possible reaction mechanism of the 5′-deoxy-5′-iodonucleosides <strong>10a</strong> and <strong>10b</strong> with AgOBz is discussed. The transformation of the xylofuranosyl moiety of <strong>14a</strong> into the ribonucleoside <strong>20a</strong> was performed on the basis of the ring-opening of the <em>O</em><sup>2</sup>,2′-anhydronucleoside <strong>24</strong> with benzoate ion. In this study, 4′-methylsulfanylcytidine <strong>26</strong> was also synthesized.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"179 ","pages":"Article 134581"},"PeriodicalIF":2.1,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143738019","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}
TetrahedronPub Date : 2025-03-21DOI: 10.1016/j.tet.2025.134605
Soumyadip Malik , Amrit Krishna Mitra
{"title":"Conduritols: Synthesis strategies from classic to contemporary","authors":"Soumyadip Malik , Amrit Krishna Mitra","doi":"10.1016/j.tet.2025.134605","DOIUrl":"10.1016/j.tet.2025.134605","url":null,"abstract":"<div><div>Conduritols, cyclic polyols with diverse biological activities, have garnered significant attention since their discovery over a century ago. These compounds, comprising six isomers (A, B, C, D, E, and F), possess unique structural and stereochemical properties, with only A and F naturally occurring. Conduritols and their derivatives serve as essential precursors for biologically significant molecules, including cyclitols, pseudo-sugars, and phosphorylated inositols. Their applications span a wide range of biological processes, such as glycosidase inhibition, insulin modulation, and signal transduction, making them promising candidates for therapeutic interventions in diabetes, cancer, and HIV/AIDS.</div><div>Synthetic advancements have enabled the preparation of all conduritol isomers, employing innovative approaches like aromatic diol transformations and stereocontrolled reactions. These methods have unlocked efficient pathways to biologically potent compounds, including pancratistatin, narciclasine, and aminoglycosidic antibiotics. This review provides an overview of the historical progress, synthetic methodologies, and biological significance of conduritols. Recent innovations in stereospecific synthesis are highlighted, showcasing the potential for large-scale production of optically pure conduritols to meet growing biomedical demands. This study aims to highlight advancements in conduritol synthesis, focusing on evolving methodologies and stereoselectivity challenges.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"178 ","pages":"Article 134605"},"PeriodicalIF":2.1,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143686418","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}
TetrahedronPub Date : 2025-03-21DOI: 10.1016/j.tet.2025.134609
Hong-Ling Pan, Han-Han Kong, Ming-Wu Ding
{"title":"One-pot synthesis of 3,4-dihydroisoquinolin-1(2H)-ones via a sequential Ugi-4CR and nucleophilic substitution reaction","authors":"Hong-Ling Pan, Han-Han Kong, Ming-Wu Ding","doi":"10.1016/j.tet.2025.134609","DOIUrl":"10.1016/j.tet.2025.134609","url":null,"abstract":"<div><div>A new one-pot preparation of 3,4-dihydroisoquinolin-1(2<em>H</em>)-ones by a sequential Ugi-4CR and nucleophilic substitution reaction has been developed. The reactions of readily available sulfonium salts, arylglyoxals, primary amines and isocyanides produced the 3,4-dihydroisoquinolin-1(2<em>H</em>)-ones in 48–86 % yields via a tandem Ugi condensation and intramolecular nucleophilic substitution at room temperature in the presence of NEt<sub>3</sub>.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"178 ","pages":"Article 134609"},"PeriodicalIF":2.1,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143697100","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}