Tetrahedron最新文献

{"title":"Synthesis, characterization and evaluation of the optical properties of novel meso-thienyl-4,4-diphenyl-BODIPY derivatives in solid state","authors":"Sandra M. Rojas-Montoya ,&nbsp;Luis Blancarte-Carrazco ,&nbsp;Rodrigo Gutiérrez-Nieto ,&nbsp;Carlos Gabriel Figueroa ,&nbsp;Oscar González-Antonio ,&nbsp;Abiut E. López-Ruiz ,&nbsp;Jesús Rodríguez-Romero ,&nbsp;Rosa Santillan ,&nbsp;Norberto Farfán","doi":"10.1016/j.tet.2025.134631","DOIUrl":"10.1016/j.tet.2025.134631","url":null,"abstract":"<div><div>In this work, we report the synthesis of new meso-thienyl-BODIPY monomers with phenyl groups as substituents on the boron atom using a novel and strategic methodology to introduce directly the BPh₂ motif by coordination of the dipyrromethene with diphenylborinic acid. A new BODIPY dimer was then obtained from the monomeric unit via Glaser coupling as the most efficient method. These compounds were deposited on FTO-coated glass substrates via spin coating. A thorough characterization of the optical properties, both in solution and in the solid state, was carried out, revealing significant changes depending on the aggregation state of the material. The studied compounds showed no significant solvatochromic effect in absorption but exhibited varying emission intensities depending on the solvent. This is attributed to the interplay of intramolecular and intermolecular charge transfer, as shown by TDDFT calculations. A reaction mechanism for the coordination step involving borinic acid is also proposed, supported by computational data. Additionally, the thermal stability and air resistance were evaluated, showing remarkable stability of the dimer compared to the monomer, confirming it as a strong candidate for applications requiring temperature variations and prolonged exposure to air. Furthermore, a morphological analysis was conducted using AFM, revealing a dendritic surface in the dimer films, which contributed to higher surface roughness. Due to the high stability demonstrated by the new BODIPY dimer, it may be a suitable candidate for its use in optoelectronic devices and other fields of science and technology.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"179 ","pages":"Article 134631"},"PeriodicalIF":2.1,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143768438","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":"Development of a scalable synthesis of RORγt inverse agonist, BMT-399150","authors":"Roshan Y. Nimje ,&nbsp;Premsai Rai Neithnadka ,&nbsp;Sivakumar Ganesan ,&nbsp;Prakasam Kuppusamy ,&nbsp;Rajesh Krishnan ,&nbsp;Dyamanna Doddalingappa ,&nbsp;M.G. Chidananda ,&nbsp;T.G. Murali Dhar ,&nbsp;Arvind Mathur ,&nbsp;Anuradha Gupta","doi":"10.1016/j.tet.2025.134617","DOIUrl":"10.1016/j.tet.2025.134617","url":null,"abstract":"<div><div>The work outlined in this manuscript describes a scalable route to the RORγt inverse agonist BMT-399150 (<strong>1</strong>), starting from readily available cyclohexane-1,3-dione. The developed process encompasses an efficient synthesis of azatricyclic amine core (<strong>13</strong>) and the use of Ullman's conditions to install the heptafluoroisopropyl moiety. The synthesis of chiral intermediate (<em>S</em>)-2-hydroxy-2-methyl-3-(methylsulfonyl)propanoic acid (<strong>18b</strong>) was achieved from readily available benzyl methacrylate. Various synthetic routes were explored to accomplish a scalable protocol to access the title compound <strong>1</strong>. This advancement enabled a competent route to the title compound in safe, cost-effective, and scalable manner.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"179 ","pages":"Article 134617"},"PeriodicalIF":2.1,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143748589","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":"Pd(II)-catalyzed double C–H activation of 1-aryl-7-azaindoles for the rollover annulation of γ-hydroxy-α,β-acetylenic esters","authors":"P. KrishnaRao ,&nbsp;Srinivasa Rao Kancharla ,&nbsp;Rajashaker Bantu ,&nbsp;A Venkat Narsaiah ,&nbsp;B. Sridhar ,&nbsp;B.V. Subba Reddy","doi":"10.1016/j.tet.2025.134622","DOIUrl":"10.1016/j.tet.2025.134622","url":null,"abstract":"<div><div>A diverse range of polycyclic azaindole frameworks has been synthesized from 1-aryl-7-azaindoles and γ-hydroxy-α,β-acetylenic esters using a catalytic amount of Pd(OAc)₂and 2 equiv Cu(OAc)₂. This is the first report on the rollover C–H annulation of 1-aryl-7-azaindoles with γ-hydroxy-α,β-acetylenic esters. This method provides a direct access to angularly fused azaindoles that are closely resemble to biologically active structural scaffolds.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"179 ","pages":"Article 134622"},"PeriodicalIF":2.1,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143738068","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":"Diterpenoids from the aril of Torreya grandis and their cytotoxicity","authors":"Jun-Ru Guo ,&nbsp;Min-Jian Dong ,&nbsp;Cheng-Xin Sun ,&nbsp;Jun Dai ,&nbsp;Mao-Sheng Zhang ,&nbsp;Shi-Ji Xiao","doi":"10.1016/j.tet.2025.134621","DOIUrl":"10.1016/j.tet.2025.134621","url":null,"abstract":"<div><div>Three new diterpenoids (<strong>2</strong>, <strong>3</strong>, and <strong>5</strong>), two new natural products (<strong>1</strong> and <strong>7</strong>), along with three analogues were isolated from the aril of <em>Torreya grandis</em>. The structural elucidation of these compounds was achieved through detailed NMR analysis, and the absolute configurations were confirmed using ECD techniques. The NMR data of 8<em>β</em>,18-dihydroxy-9(11),13-abietadien-12-one (<strong>6</strong>) was revised. The cytotoxic effects of the isolated compounds on SW1990, A549, MDB-MA-231, and HCT116 cells were evaluated using the MTT assay.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"178 ","pages":"Article 134621"},"PeriodicalIF":2.1,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143724277","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":"Five new cantharidin derivatives from the insect Mylabris cichorii and their potential for the treatment of neuroinflammatory diseases","authors":"Ke-Ming Li ,&nbsp;Wei-Fen Li ,&nbsp;Madhu Babu Sura ,&nbsp;Guangyi Yang ,&nbsp;Yong-Xian Cheng","doi":"10.1016/j.tet.2025.134624","DOIUrl":"10.1016/j.tet.2025.134624","url":null,"abstract":"<div><div>Five previously undescribed monoterpenoids, including two 1,2-dimethyl cantharimide-type derivatives (<strong>1</strong> and <strong>2</strong>), one 1-hydroxymethyl-2-methyl cantharimide-type derivative (<strong>3</strong>), and two 1-methyl cantharimide-type derivatives (<strong>4</strong> and <strong>5</strong>), were isolated from the whole bodies of <em>Mylabris cichorii</em> L. Their structures, including absolute configurations, were identified using 1D and 2D NMR, HRESIMS, and electronic circular dichroism (ECD) calculations. Considering the role of cantharidin derivatives in anti-neuroinflammation, all the compounds were evaluated for their neuroinflammatory activities. Results showed that compound <strong>2</strong> ameliorated LPS-induced neuroinflammation and reduced oxidative stress by targeting mitochondria, thereby decreasing reactive oxygen species (ROS) and pro-inflammatory cytokines. This suggests that compound <strong>2</strong> may be useful in treating neuroinflammatory diseases.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"178 ","pages":"Article 134624"},"PeriodicalIF":2.1,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143725827","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":"Isolation and chemical structure elucidation of a new praziquantel degradant and BHT crosslinked impurity in a liquid finished drug product","authors":"Jiangtao He,&nbsp;Abu Rustum","doi":"10.1016/j.tet.2025.134623","DOIUrl":"10.1016/j.tet.2025.134623","url":null,"abstract":"<div><div>During the stability test of a liquid finished drug product (topical liquid transdermal formulation), an unexpected unknown peak was observed in the High Performance Liquid Chromatography (HPLC) chromatogram. This finished drug product is used to control mixed infestations of ectoparasites, nematodes, and cestodes in cats. This topical liquid drug product contains three active pharmaceutical ingredients (APIs), esafoxolaner, eprinomectin, and praziquantel. The identity of any new unknown peak (above certain threshold) in any given finished product batch must be established to ensure that the unknown peak is correctly estimated against the parent compound (API). As there are three APIs in this product, an incorrect assignment of the origin and identity of any given impurity will cause either overestimation or underestimation of the impurity, including misleading information on safety. Therefore, the chemical structure and the correct origin/source(s) of this unknown peak need to be determined. Although High Resolution Mass Spectrometry (HRMS) provides valuable information for determining the structure of the impurity associated with this peak, its structure cannot be fully established by HRMS data alone. Hence, this impurity peak was isolated and purified from aged finished drug product stability samples by semi-prep HPLC. Its chemical structure was fully elucidated through Nuclear Magnetic Resonance (NMR) (¹H, ¹³C, and 2D). The results revealed that the impurity was formed through a cross-reaction between a praziquantel degradant and butylated hydroxytoluene (BHT), which is used as an antioxidant in the finished drug product. The experimental details and full structure elucidation data and related information of this unexpected new degradation product peak is reported in this paper. The mechanism of formation of this impurity is proposed based on its positively identified chemical structure. Based on an extensive literature search, it can be concluded that this is the first known report on the definitive identification of the chemical structure and formation mechanisms of this impurity.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"178 ","pages":"Article 134623"},"PeriodicalIF":2.1,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143704605","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":"Synthesis and evaluation of new isoquinoline diimide derivatives as small molecule acceptors for organic solar cells","authors":"Alberto Insuasty ,&nbsp;Serena Carrara ,&nbsp;Doan Vu ,&nbsp;Joel José Montalvo-Acosta ,&nbsp;Alejandro Ortíz ,&nbsp;Conor Hogan ,&nbsp;Christopher R. McNeill ,&nbsp;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}

{"title":"Studies toward the synthesis of yaretol: an unexpected rearrangement en route to the tricyclic core","authors":"C. Elizabeth Adams,&nbsp;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}

{"title":"Synthesis of the ACDE tetracyclic skeleton in ceforalide B","authors":"Xiao-Wei Cong ,&nbsp;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)₃-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}

{"title":"Visible-light-driven synthesis of benzoxepine derivatives from aromatic diazo compounds","authors":"Xiuyuan Duan,&nbsp;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}