{"title":"Alkoxy Substitution Controls Columnar Organization in Quinoxaline Cyclotetrabenzoin Macrocycles","authors":"Ashikur Rahman Rabbi, Sandipan Ghorai, Asmita Shah, Suraj Kumar Pathak, Torsten Hegmann, Ognjen Š Miljanić","doi":"10.1021/acs.joc.6c00924","DOIUrl":"10.1021/acs.joc.6c00924","url":null,"abstract":"<p>Shape-persistent quinoxaline macrocycles were synthesizedfromcyclotetrabenzil through condensations with substituted phenylenediamines.Variation of peripheral alkoxy substituents systematically modulatessupramolecular organization in the solid state. Selected tetraalkoxymacrocycles form ordered soft crystal columnar hexagonal phases, whereasoctaalkoxy derivatives exhibit more diverse phase behavior. Notably,a branched 3,7-dimethyloctyl derivative displays a columnar obliqueliquid-crystalline phase. Single-crystal structures reveal layeredpacking governed primarily by weak [C–H···O],[C–H···N], and [C–H···π]interactions. These results demonstrate that macrocycle size and side-chainarchitecture influence columnar packing and phase behavior in quinoxalinemacrocycles, with the branched octaalkoxy derivative uniquely exhibitinga liquid-crystalline mesophase.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"91 41","pages":"13565–13575"},"PeriodicalIF":3.3,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149088166","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Unexpected Rearrangement of Unsaturated Lactones to Give Tricyclic Furopyrrolidinones","authors":"Ebuka L. Onyeyilim, David B. C. Martin","doi":"10.1021/acs.joc.6c01880","DOIUrl":"10.1021/acs.joc.6c01880","url":null,"abstract":"<p>An unexpected cyanide-mediated rearrangement of conjugatedlactonesis described, providing access to novel tricyclic furopyrrolidinones.This reaction occurs in a stoichiometry- and substrate-dependent manner,induced by multiple additions of cyanide to α,β,γ,δ-unsaturatedlactones bearing suitable aryl substituents, providing products withadjacent ether, nitrile, and lactam functionalities. Single-crystalX-ray diffraction (SCXRD) studies of two products support the stereochemicalassignments, providing evidence of a dynamic equilibrium process.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"91 41","pages":"13806–13811"},"PeriodicalIF":3.3,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149088169","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yu-Wei Jiang, Jia-Di Ren, Li-Xue Zhou, Hui Gao, Pei-Long Wang
{"title":"Electrochemical One-Pot Diverse C(sp3)–X Bond (Including C–H, C–C, C–N, and C–O) Transformations and C(sp2)–H Acyloxylation of Alkylarenes","authors":"Yu-Wei Jiang, Jia-Di Ren, Li-Xue Zhou, Hui Gao, Pei-Long Wang","doi":"10.1021/acs.joc.6c01447","DOIUrl":"10.1021/acs.joc.6c01447","url":null,"abstract":"<p>In this study, an electrochemicalone-pot cleavage ofdiverse C(sp<sup>3</sup>)–X bonds and acyloxylation of C(sp<sup>2</sup>)–Hwere reported. Based on the experimental results, we discovered forthe first time that NH<sub>3</sub> can strongly promote electrolytedissolution and significantly increase the conductivity of a solution.Unlike previous C(sp<sup>2</sup>)–H acetoxylation reactionsin which AcO<sup>–</sup> functions as a nucleophile, this reactionundergoes an acetoxy radical mechanism and prevents decarboxylationof the acetoxy radical. This reaction is advantageous because it istransition-metal-free, external-oxidant-free, atom- and step-economical,and applicable to diverse substrates; additionally, it uses mild reactionconditions and green and nontoxic solvents.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"91 41","pages":"13650–13656"},"PeriodicalIF":3.3,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149088171","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Dual-State Fluorescence with Efficiency Close to Unity from D-π-A-Type Triarylborane-Based Naphthalenes","authors":"Min Wang, Meng-Qi Wu, Yi Fang, Cui-Hua Zhao","doi":"10.1021/acs.joc.6c00979","DOIUrl":"10.1021/acs.joc.6c00979","url":null,"abstract":"<p>Fluorophores exhibiting bright fluorescence in both dilutesolutionand the solid state, termed dual-state emission (DSE), are more attractivefor practical applications than those that fluoresce in a single state.Herein, we disclose two DSE-active naphthalene derivatives, <strong>BNPh-Nap</strong> and <strong>BNOPh-Nap</strong>, featuring a simple D-π-Astructure with an electron-accepting dimesitylboryl (BMes<sub>2</sub>) and electron-donating diphenylamino (NPh<sub>2</sub>) or <em>N</em>,<em>N</em>’-di(4-methoxyphenyl)amino (N<sup>OMe</sup>Ph<sub>2</sub>) substituents at the 2,6-positions of thenaphthalene core unit. Despite the very flat structure of the naphthalenecore unit, the steric hindrance of the BMes<sub>2</sub> and diarylaminogroups can effectively suppress intermolecular π-π interactionsin the solid state. As a result, <strong>BNPh-Nap</strong> exhibits strongfluorescence not only in solution (Φ<sub>F</sub> = 0.97 in cyclohexane)but also in the solid state, including powder (Φ<sub>F</sub> = 0.67) and neat film (Φ<sub>F</sub> = 0.51). From <strong>BNPh-Nap</strong> to <strong>BNOPh-Nap</strong>, although the fluorescence efficiencydecreases slightly in solution (Φ<sub>F</sub> = 0.71 in cyclohexane),the enhanced electron-donating ability of the amino group greatlyboosts the solid-state fluorescence, yielding near-unity Φ<sub>F</sub> values in both powder (Φ<sub>F</sub> = 0.91) and film(Φ<sub>F</sub> = 0.99). These results demonstrate that simplemodification of a conventional planar π-core with BMes<sub>2</sub> and diarylamino groups enables high-performance DSE without complextwisted architectures, providing an effective strategy for developingDSE-active fluorophores.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"91 41","pages":"13576–13583"},"PeriodicalIF":3.3,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149088165","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Anthony T. Saucedo, Brian Valladares, David A. Delgadillo, Hosea M. Nelson, Alison R. H. Narayan
{"title":"Chemoenzymatic Synthesis of (E,E,Z)-Humulene-Derived Natural Products","authors":"Anthony T. Saucedo, Brian Valladares, David A. Delgadillo, Hosea M. Nelson, Alison R. H. Narayan","doi":"10.1021/acs.joc.6c01732","DOIUrl":"10.1021/acs.joc.6c01732","url":null,"abstract":"<p>Meroterpenoid naturalproducts derived from the 11-membered macrocyclehumulene are of great interest due to their potent biological activitiesand intricate architectures. Whereas molecules derived from the mostavailable (<em>E</em>,<em>E</em>,<em>E</em>)-humulene isomer have been thoroughly investigated, little is knownof the chemistry and biological properties of natural products derivedfrom the (<em>E</em>,<em>E</em>,<em>Z</em>)-isomer and derivatives thereof. Herein, we detail the first synthesisof (<em>E</em>,<em>E</em>,<em>Z</em>)-(10<em>S</em>)-hydroxyhumulene through a selective oxidative double-bondisomerization, and using this key building block along with (<em>E</em>,<em>E</em>,<em>Z</em>)-humulene, a suiteof complex meroterpenoids was synthesized, including (±)-deoxynoreupenifeldinand neosetophomone B through a chemoenzymatic strategy and pughiininA through a non-enzymatic route. In addition to gaining syntheticaccess to a suite of (<em>E</em>,<em>E</em>,<em>Z</em>)-humulene-derived natural products, this work revealedreactivity differences between (<em>E</em>,<em>E</em>,<em>E</em>)-humulene and its (<em>E</em>,<em>E</em>,<em>Z</em>)-isomer. Overall, these efforts culminatein the first total syntheses of three (<em>E</em>,<em>E</em>,<em>Z</em>)-humulene-derived natural products,providing access to this untapped subset of secondary metabolites.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"91 41","pages":"13702–13709"},"PeriodicalIF":3.3,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149088570","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Cobalt-Catalyzed Azidation of Benzylic C–H Bonds","authors":"Peng-Fei Wang, Xiang Wang, Yan-Qing Zeng, Bing-Fa Xiang, Li-Hua Zhao, Jing Chen, Xian-Heng Song, Ya-Jun Wang","doi":"10.1021/acs.joc.6c01153","DOIUrl":"https://doi.org/10.1021/acs.joc.6c01153","url":null,"abstract":"<p>Direct methods for selective functionalizationof C(sp<sup>3</sup>)–H bonds could greatly streamline the synthesisof complexmolecules. However, such transformations remain challenging. Herein,we report a cobalt-catalyzed azidation of benzylic C–H bondsthat enables efficient access to benzylic azides. The reaction employsthe C–H substrate as the limiting reagent and features broadsubstrate scope, as well as good functional-group tolerance. The keyto success lies in the utilization of a commercially available <em>N</em>,<em>N</em>-ligand and cobalt catalyst. Preliminarymechanistic study indicates that hydrogen-atom transfer (HAT) of benzylicC–H bonds affords a benzyl radical that is involved in thereaction process.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"91 41","pages":"13603–13608"},"PeriodicalIF":3.3,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149188025","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Max Schönenbroicher, Florian Heppner, Maximilian Seul, Simon Morgenschweis, Dirk Menche
{"title":"Convergent Synthesis of a Desmethyl Analogue of Amycomycin","authors":"Max Schönenbroicher, Florian Heppner, Maximilian Seul, Simon Morgenschweis, Dirk Menche","doi":"10.1021/acs.joc.6c01817","DOIUrl":"https://doi.org/10.1021/acs.joc.6c01817","url":null,"abstract":"<p>The convergent synthesis of a desmethyl analogue of amycomycin,the aglycon of vancoresmycin, is presented. The central challengeof the convergent strategy was an initial aldol condensation approach,which failed on advanced substrates due to steric hindrance, promptinga revised coupling strategy. The successful route employed nucleophilicvinyl addition, complemented by a Boron-Wittig olefination to constructsterically congested vinyl boronates. A late-stage <em>O</em>- to <em>C</em>-acyl transfer on a complex 3-acyl tetramicacid was essential for the efficient assembly of the complete skeletonof desmethyl amycomycin.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"91 41","pages":"13749–13757"},"PeriodicalIF":3.3,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173850","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Brønsted Acid-Catalyzed\u0000Nitroso-Diels–Alder\u0000Reaction of 2-Trifluoroacetamido-1,3-dienes","authors":"Qin Luo,Shi-Yao Kong,Xiao-Hui Chang,Gongde Wu,Long-Wu Ye,Xin-Qi Zhu","doi":"10.1021/acs.joc.6c01258","DOIUrl":"https://doi.org/10.1021/acs.joc.6c01258","url":null,"abstract":"Abstract The nitroso-Diels–Alder (NDA) reaction represents a powerful strategy for the assembly of 3,6-dihydro-1,2-oxazines for nearly a century, owing to its efficiency and broad utility in synthesizing natural products and bioactive molecules. Despite these advancements, traditional NDA reactions are largely limited to neutral 1,3-dienes, while electron-rich 1,3-dienes bearing heteroatom substitutions remain underdeveloped. Herein, we report a Brønsted acid-catalyzed NDA reaction of electron-rich 2-trifluoroacetamido-1,3-dienes with nitrosobenzenes, delivering diverse dihydro-2H-1,2-oxazines in excellent yields. This protocol represents the first NDA reaction of 2-trifluoroacetamido-1,3-dienes.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"14 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210341","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}