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

{"title":"Theoretical study on the CoII/CoIII and CoII/CoIV catalytic cycles in CoII(salen)-catalyzed radical fluorination with various different NF-type fluorinating reagents","authors":"Jingwen Li,&nbsp;Mong-Feng Chiou,&nbsp;Hongli Bao","doi":"10.1039/d6qo00260a","DOIUrl":"10.1039/d6qo00260a","url":null,"abstract":"<div><div>Co^II(salen)-catalyzed radical fluorination provides a mild and efficient approach for the construction of carbon–fluorine bonds. However, the mechanistic role of different NF-type fluorinating reagents and the corresponding catalytic cycle pathways (Co^II/Co^III<em>vs.</em> Co^II/Co^IV) in the Co^II(salen)-catalyzed fluorination system remain controversial. Therefore, this work employs density functional theory (DFT) to computationally analyze the reaction mechanisms of radical fluorination involving three classes of NF-type fluorinating reagents: <em>N-tert</em>-butylfluoramide, <em>N</em>-ethyl-<em>N</em>-fluorobenzenesulfonamide, and Me₃NFPy·BF₄. The results indicate that the nature of the NF-type fluorinating reagent exerts a decisive influence on the reaction pathway. <em>N-tert</em>-butylfluoramide and <em>N</em>-ethyl-<em>N</em>-fluorobenzenesulfonamide tend to undergo single-electron oxidation with Co^II(salen), generating Co^III(salen)–F and the corresponding amidyl radical, with the reaction proceeding <em>via</em> a Co^II/Co^III cycle. In contrast, Me₃NFPy·BF₄ favors a two-electron oxidation process, directly forming the [Co^IV(salen)–F]⁺ intermediate, and the reaction proceeds through a Co^II/Co^IV cycle. Furthermore, for the hydrofluorination of unactivated alkenes involving Me₃NFPy·BF₄, the calculations not only clearly elucidate the formation pathway of Co^III(salen)–H but also confirm that the occurrence of Wagner–Meerwein rearrangement in the product is related to the presence of a substituent at the benzylic position of the substrate. Through theoretical calculations, this study provides a unified theoretical analysis of the roles of different NF-type fluorinating reagents in the Co^II(salen)-catalyzed fluorination system, offering an important theoretical basis for the rational design and condition optimization of future cobalt-catalyzed fluorination reactions.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 13","pages":"Pages 4003-4014"},"PeriodicalIF":0.0,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148503370","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}

{"title":"Aluminium-catalysed carbonyl-selective hydrophosphinylation of α,β-unsaturated ketones","authors":"Ziyuan Pang,&nbsp;Wen Dai,&nbsp;Xiaobo Yang,&nbsp;Xiaoli Ma,&nbsp;Hongping Zhu,&nbsp;Zhi Yang","doi":"10.1039/d6qo00397d","DOIUrl":"10.1039/d6qo00397d","url":null,"abstract":"<div><div>An aluminium-catalysed carbonyl-selective hydrophosphinylation of α,β-unsaturated ketones is reported herein. Among the synthesised Schiff-base-supported non-precious metal complexes, the aluminium hydride complex exhibited outstanding catalytic activity. In contrast to conventional systems that favour conjugate addition, this catalytic system enables selective addition of dimethyl phosphine oxide to the carbonyl group, thereby altering the inherent regioselectivity of these substrates. Under mild conditions, a wide range of α,β-unsaturated ketones were efficiently converted to the desired products, and double hydrophosphinylation could also be achieved through adjustment of the reagent stoichiometry. DFT calculations provided further insight into the reaction mechanism and support a stepwise aluminium-assisted carbonyl activation pathway involving key Al–O–P intermediates. This work provides an efficient and sustainable strategy for selective C–P bond construction using main-group-metal catalysis.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 13","pages":"Pages 4109-4117"},"PeriodicalIF":0.0,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148503283","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}

{"title":"Recent advances in transition metal-catalyzed organic transformations using hemilabile P,PO ligands","authors":"Zhenming Zhang,&nbsp;He Yang,&nbsp;Wenjun Tang","doi":"10.1039/d6qo00360e","DOIUrl":"10.1039/d6qo00360e","url":null,"abstract":"<div><div>Bisphosphine monoxides (BPMOs) represent a distinctive class of hemilabile bidentate ligands featuring a trivalent phosphine as a soft coordination site, combined with a hard coordination site in the form of P(<span>v</span>)O; hence, they are referred to as P,PO ligands. Despite their potential benefits, including their ability to regulate a variety of elementary steps essential in transition metal-enabled organic reactions, such as ligand exchange, isomerization, oxidative addition, migratory insertion, and reductive elimination, the P,PO ligands have not garnered significant attention compared with other hemilabile ligands and bidentate phosphine ligands in the past decades. This limited recognition is due to challenges associated with their synthesis methods and their inconspicuous presence within high-valent transition-metal/bidentate phosphine ligand catalytic systems under basic or oxygen-containing conditions. The incorporation of the P,PO ligands in transition metal-catalyzed organic reactions offers a pathway characterized by low activation energy for a diverse range of reactions. Herein, this review article provides a comprehensive overview of the utilization of the BPMO ligands in transition metal-catalyzed organic transformations from around 2004 to date, encompassing addition reactions, alkene functionalization reactions, coupling reactions, [4 + 2] cycloadditions, C–H functionalizations, and other transformations.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 13","pages":"Pages 4138-4173"},"PeriodicalIF":0.0,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148503286","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}

{"title":"Enantiodivergent difluoroalkylation of alkenes via photoenzymatic catalysis","authors":"Jiafan Xu,&nbsp;Zhuanglin Shen,&nbsp;Hongkui Wang,&nbsp;Yuxiang Gao,&nbsp;Jiangtao Gao,&nbsp;Jiahai Zhou,&nbsp;Yang Gu","doi":"10.1039/d6qo00279j","DOIUrl":"10.1039/d6qo00279j","url":null,"abstract":"<div><div>Fluorinated compounds are extensively utilized in pesticides, pharmaceuticals, and materials. Despite significant advances in synthetic methodologies, the stereocontrolled installation of chiral fluorinated motifs remains a formidable challenge. Here, we report the photoenzymatic enantiodivergent synthesis of difluoroalkyl compounds using bromodifluoromethyl phenyl sulfone. Through a highly controlled asymmetric hydrogen atom transfer process catalyzed by two different photoenzymes, both enantiomers of the products are obtained (up to 99% ee). This photoenzymatic system demonstrates broad substrate scope, indicating its potential for use in the synthesis of chiral difluoroalkyl compounds. Radical clock experiments and deuterium labeling studies demonstrate the generation of radical species during this reaction process, and the asymmetric hydrogen atom transfer step is shown to be cofactor-mediated. Furthermore, computer simulations elucidated the selectivity of different olefin reductases toward products with distinct conformations. Our work has successfully introduced difluoromethylsulfonyl groups into organic small molecules, advancing the development of enzyme-catalyzed fluorinated alkylation strategies and revealing a novel route for the radical-mediated asymmetric synthesis of chiral difluoroalkyl compounds that are otherwise difficult to access through conventional chemical approaches.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 13","pages":"Pages 3976-3985"},"PeriodicalIF":0.0,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148503367","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}

{"title":"Bifunctional para-quinone methides in organocatalytic [3 + 2]-annulation with nitroalkenes: enantio- and diastereoselective assembly of nitrogen-functionalized cyclopentanes","authors":"Yulia A. Antonova,&nbsp;Andrey A. Tabolin","doi":"10.1039/d6qo00439c","DOIUrl":"10.1039/d6qo00439c","url":null,"abstract":"<div><div>Densely substituted nitrogen-functionalized cyclopentanes are ubiquitous structural motifs in many bioactive compounds, yet their synthesis remains challenging due to inherent molecular complexity. Asymmetric organocatalytic domino reactions can provide direct access to these scaffolds through quick and effective construction of several bonds in one operational step. Herein, we report an enantio- and diastereoselective [3 + 2]-annulation of bifunctional malonate-possessing <em>para</em>-quinone methides and nitroalkenes, leading to nitro-substituted cyclopentanes with three contiguous stereocenters. This reaction proceeds under mild conditions, tolerates a wide range of functionalities, and allows an efficient gram-scale synthesis. The developed strategy introduces a novel reactivity pattern for stable quinone methides, based on their use as three-carbon synthons. Telescopic one-pot synthesis of nitrocyclopentanes from simple starting materials was achieved through an effective catalytic cyclopropanation/annulation sequence. Chemoselective modifications of the obtained products led to the chiral cyclopentene derivatives and 2-azabicyclo[2.2.1]heptane, a privileged scaffold for medicinal chemistry.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 13","pages":"Pages 3986-4002"},"PeriodicalIF":0.0,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148503368","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}

{"title":"Nickel-catalyzed stereo-controlled C–F activation for the synthesis of monofluoroalkenyl C-glycosides","authors":"Renjie Zhang,&nbsp;Yanchen Yang,&nbsp;Baiyang Li,&nbsp;Zhiyang Xu,&nbsp;Pengfei Wang,&nbsp;Shengbin Zhou,&nbsp;Hong Liu,&nbsp;Chunpu Li","doi":"10.1039/d6qo00243a","DOIUrl":"10.1039/d6qo00243a","url":null,"abstract":"<div><div>The monofluoroalkene moiety serves as a metabolically stable bioisostere of amide bonds, and <em>C</em>-glycosides offer improved pharmacokinetic properties compared to glycan mimetics. Consequently, monofluoroalkenyl <em>C</em>-glycosides, which merge the benefits of both structural motifs, have emerged as highly valuable scaffolds in medicinal chemistry. However, stereocontrolled synthetic access to monofluoroalkenyl <em>C</em>-glycosides still remains challenging. Herein, we report a nickel-catalyzed asymmetric C–F bond activation strategy for the direct and stereocontrolled synthesis of these valuable scaffolds <em>via</em> the coupling of glycosyl bromides with <em>gem</em>-difluoroalkenes. This method leverages an ester directing group to govern stereoselective C–F cleavage, affording monofluoroalkenyl glycosides in good yields with excellent <em>E</em>-selectivity and high α-selectivity. The reaction exhibits broad substrate compatibility, accommodating diverse glycosyl donors and a wide range of <em>gem</em>-difluoroalkenes. Its synthetic utility is demonstrated through the late-stage functionalization of complex pharmaceuticals and natural product derivatives. Mechanistic investigations support a pathway involving a Ni(<span>i</span>)/Ni(<span>ii</span>)/Ni(<span>iii</span>) catalytic cycle with the glycosyl radical intermediates. This work establishes a general and stereocontrolled catalytic approach to monofluoroalkene-based <em>C</em>-glycosidic linkages, providing a new avenue for selective fluorinated modification in drug discovery.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 13","pages":"Pages 3944-3951"},"PeriodicalIF":0.0,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148503372","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}

{"title":"Repurposing trichloroacetonitrile as a sustainable radical synthon for regiodivergent photocatalytic alkene amination","authors":"Xinlin Wang,&nbsp;Zhikai Li,&nbsp;Jia Jin,&nbsp;Kui Zhang,&nbsp;Lingchao Cai","doi":"10.1039/d6qo00456c","DOIUrl":"10.1039/d6qo00456c","url":null,"abstract":"<div><div>Persistent endeavors have been dedicated to the synthesis of nitrogen-containing compounds, which hold paramount significance in biological processes and are indispensable in the realms of pharmaceuticals and advanced materials. Herein, an innovative photocatalytic radical relay strategy has been devised for the regiodivergent amination of alkenes utilizing trichloroacetonitrile (CCl₃CN) as an N-centered radical precursor, diverging from its classical electrophilic reactivity. This method leveraged the inherent weakness of the N–O bond in an oxime-imidate reagent to generate electrophilic amidyl radicals <em>via</em> oxy-radical isomerization, without gaseous byproducts, and enabling three distinctive amination pathways: 1,2-diamination, a three-component radical-relay assembly of 1,4-diamines from two distinct olefins, and anti-Markovnikov hydroamination of alkenes. The CCl₃ group plays a pivotal role in modulating the reactivity of amidyl radical intermediates through its electron-withdrawing effects, while also demonstrating compatibility with further functionalization <em>via</em> boryl radical chemistry. This work repositions a legacy electrophile as a multifaceted radical synthon, offering a general strategy for modular nitrogen incorporation in complex molecule synthesis.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 13","pages":"Pages 4070-4077"},"PeriodicalIF":0.0,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148503376","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}

{"title":"A chiral multibrominated triangular macrocycle for modulating circularly polarized phosphorescence","authors":"Yuluo Huang,&nbsp;Jianqiu Li,&nbsp;Ming-Ze Meng,&nbsp;Tuo-Yu Zhou,&nbsp;Xiao-Nian Xue,&nbsp;Huang Wu,&nbsp;Shanshan Cheng,&nbsp;Yu Wang","doi":"10.1039/d6qo00378h","DOIUrl":"10.1039/d6qo00378h","url":null,"abstract":"<div><div>Pure organic circularly polarized room-temperature phosphorescence (CP-RTP) materials hold great promise for applications in bioimaging and information encryption. However, achieving CP-RTP with tunable emission colors remains a formidable challenge. Herein, we present a novel approach for constructing tunable CP-RTP materials utilizing a macrocyclic supramolecular strategy. We synthesized a pair of chiral triangular macrocyclic enantiomers, (6<em>R</em>/<em>S</em>)-PMDI, <em>via</em> the condensation of (<em>R</em>,<em>R</em>)- or (<em>S</em>,<em>S</em>)-<em>trans</em>-1,2-diaminocyclohexane with 1,4-dibromo-2,3,5,6-tetracarboxybenzene. The chirality of the macrocycle originates from the rigid diamine unit. This triangular macrocycle exhibits weak fluorescence in solution, and its solid powders are non-luminescent. Remarkably, doping it into a poly(methyl methacrylate) (PMMA) polymer matrix successfully achieved CP-RTP. Furthermore, supramolecular assembly of the triangular macrocycle with the electron-rich guest 9-phenylcarbazole (9-Pcbz) endowed the resulting assemblies with red CP-RTP, which can be attributed to the significant intermolecular charge-transfer (CT) interactions. The supramolecular strategy presented in this work provides an effective platform for the development of color-tunable CP-RTP materials.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 13","pages":"Pages 3923-3933"},"PeriodicalIF":0.0,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148503287","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}

{"title":"Selective radical defluorinative germylation and hydrogermylation of α-trifluoromethylalkenes","authors":"Shuoshuo Zhang,&nbsp;Haibin Xiao,&nbsp;Yanjun Wu,&nbsp;Yue Zhang,&nbsp;Ling Jin,&nbsp;Junhao Chen,&nbsp;Xiaolei Huang","doi":"10.1039/d6qo00391e","DOIUrl":"10.1039/d6qo00391e","url":null,"abstract":"<div><div>α-Trifluoromethylalkenes are pivotal scaffolds in pharmaceuticals, agrochemicals, and materials science. Recent advances have focused on their defluorinative functionalization or hydrofunctionalization with carbon- or silicon-containing coupling partners. However, as a fellow group 14 element, strategies for introducing germanium into α-trifluoromethylalkenes, most notably defluorinative germylation, remain largely underdeveloped. Herein, we describe a versatile method for the visible-light-mediated defluorinative germylation of α-trifluoromethylalkenes with germanes by the combination of organic photoredox and HAT catalysis. The organic base serves as the key factor in achieving selective conversion. When pyridine is replaced with DMAP, the reaction encounters a selectivity switch to hydrogermylation, affording the trifluoromethylalkylated germane derivatives.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 13","pages":"Pages 4045-4051"},"PeriodicalIF":0.0,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148503374","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}

{"title":"Palladium-catalyzed synthesis of aryl phosphonates using sodium hypophosphite","authors":"Dang-Wei Qian,&nbsp;Shi-Peng Chen,&nbsp;Hai-Chen Ma,&nbsp;Shang-Dong Yang","doi":"10.1039/d6qo00520a","DOIUrl":"10.1039/d6qo00520a","url":null,"abstract":"<div><div>Aryl phosphonates represent a class of crucial structural motifs widely embedded in pharmaceutical molecular frameworks. Conventional synthetic approaches typically rely on PCl₃ or P(O)Cl₃ as the phosphorus source, and face two major challenges: the inherent toxicity and instability of the phosphorus reagents and the harsh reaction conditions accompanied by tedious operational procedures. There is an increasing need for alternative phosphorus sources that are more stable, greener, and cost-effective to replace the commonly used PCl₃. Herein, we disclose a facile and efficient method for synthesizing aryl phosphonates from alcohol reagents and aryl halides, using stable, green, and readily available NaH₂PO₂ as a phosphorus source in a one-pot, multicomponent fashion that proceeds under very mild conditions for the first time. Notably, this approach not only eliminates the use of PCl₃ but also enhances both the synthetic efficiency and practical applicability of aryl phosphonates significantly.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 13","pages":"Pages 4089-4094"},"PeriodicalIF":0.0,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148503378","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}