Organic chemistry frontiers : an international journal of organic chemistry最新文献_第2页

Recent advances in transition metal-catalyzed organic transformations using hemilabile P,PO ligands 半可降解P，PO配体在过渡金属催化有机转化中的最新进展

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2026-07-01 Epub Date: 2026-05-12 DOI: 10.1039/d6qo00360e

Zhenming Zhang, He Yang, Wenjun Tang

{"title":"Recent advances in transition metal-catalyzed organic transformations using hemilabile P,PO ligands","authors":"Zhenming Zhang, He Yang, 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}

引用次数: 0

Enantiodivergent difluoroalkylation of alkenes via photoenzymatic catalysis 光酶催化烯烃的对映发散二氟烷基化

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2026-07-01 Epub Date: 2026-05-06 DOI: 10.1039/d6qo00279j

Jiafan Xu, Zhuanglin Shen, Hongkui Wang, Yuxiang Gao, Jiangtao Gao, Jiahai Zhou, Yang Gu

{"title":"Enantiodivergent difluoroalkylation of alkenes via photoenzymatic catalysis","authors":"Jiafan Xu, Zhuanglin Shen, Hongkui Wang, Yuxiang Gao, Jiangtao Gao, Jiahai Zhou, 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}

引用次数: 0

Bifunctional para-quinone methides in organocatalytic [3 + 2]-annulation with nitroalkenes: enantio- and diastereoselective assembly of nitrogen-functionalized cyclopentanes 双官能团对醌类化合物与硝化烯烃的有机催化[3 + 2]环化：氮官能团环戊烷的对映和非对映选择性组装

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2026-07-01 Epub Date: 2026-05-09 DOI: 10.1039/d6qo00439c

Yulia A. Antonova, Andrey A. Tabolin

{"title":"Bifunctional para-quinone methides in organocatalytic [3 + 2]-annulation with nitroalkenes: enantio- and diastereoselective assembly of nitrogen-functionalized cyclopentanes","authors":"Yulia A. Antonova, 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}

引用次数: 0

Nickel-catalyzed stereo-controlled C–F activation for the synthesis of monofluoroalkenyl C-glycosides 镍催化立体控制C-F活化合成单氟烯基c -糖苷

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2026-07-01 Epub Date: 2026-05-11 DOI: 10.1039/d6qo00243a

Renjie Zhang, Yanchen Yang, Baiyang Li, Zhiyang Xu, Pengfei Wang, Shengbin Zhou, Hong Liu, Chunpu Li

{"title":"Nickel-catalyzed stereo-controlled C–F activation for the synthesis of monofluoroalkenyl C-glycosides","authors":"Renjie Zhang, Yanchen Yang, Baiyang Li, Zhiyang Xu, Pengfei Wang, Shengbin Zhou, Hong Liu, 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}

引用次数: 0

Repurposing trichloroacetonitrile as a sustainable radical synthon for regiodivergent photocatalytic alkene amination 三氯乙腈作为区域发散型光催化烯烃胺化的可持续自由基合成物的再利用

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2026-07-01 Epub Date: 2026-05-16 DOI: 10.1039/d6qo00456c

Xinlin Wang, Zhikai Li, Jia Jin, Kui Zhang, Lingchao Cai

{"title":"Repurposing trichloroacetonitrile as a sustainable radical synthon for regiodivergent photocatalytic alkene amination","authors":"Xinlin Wang, Zhikai Li, Jia Jin, Kui Zhang, 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 (CCl<sub>3</sub>CN) 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 CCl<sub>3</sub> 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}

引用次数: 0

A chiral multibrominated triangular macrocycle for modulating circularly polarized phosphorescence 调制圆偏振磷光的手性多溴三角形大环

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2026-07-01 Epub Date: 2026-05-14 DOI: 10.1039/d6qo00378h

Yuluo Huang, Jianqiu Li, Ming-Ze Meng, Tuo-Yu Zhou, Xiao-Nian Xue, Huang Wu, Shanshan Cheng, Yu Wang

{"title":"A chiral multibrominated triangular macrocycle for modulating circularly polarized phosphorescence","authors":"Yuluo Huang, Jianqiu Li, Ming-Ze Meng, Tuo-Yu Zhou, Xiao-Nian Xue, Huang Wu, Shanshan Cheng, 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}

引用次数: 0

Selective radical defluorinative germylation and hydrogermylation of α-trifluoromethylalkenes α-三氟甲基烯烃的选择性自由基脱氟化和加氢化

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2026-07-01 Epub Date: 2026-05-12 DOI: 10.1039/d6qo00391e

Shuoshuo Zhang, Haibin Xiao, Yanjun Wu, Yue Zhang, Ling Jin, Junhao Chen, Xiaolei Huang

引用次数: 0

Palladium-catalyzed synthesis of aryl phosphonates using sodium hypophosphite 钯催化次亚磷酸钠合成芳基膦酸盐

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2026-07-01 Epub Date: 2026-05-12 DOI: 10.1039/d6qo00520a

Dang-Wei Qian, Shi-Peng Chen, Hai-Chen Ma, Shang-Dong Yang

引用次数: 0

Catalyst-controlled chemodivergent C–H functionalization of 2-pyridylthiophenes with allylic alcohols 催化控制的2-吡啶基噻吩与烯丙醇的化学发散C-H功能化

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2026-07-01 Epub Date: 2026-05-15 DOI: 10.1039/d6qo00441e

Guibin Wan, Qiang Zhang, Ying Liu, Haowei Zeng, Taoyuan Liang, Shuangliang Zhao, Zhuan Zhang

引用次数: 0

Synthesis of fluorescent cyclopentene-fused-phenanthrenes via boron trifluoride-promoted cascade cationic cyclization 三氟化硼催化级联阳离子环化合成荧光环戊烯-菲

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2026-07-01 Epub Date: 2026-05-06 DOI: 10.1039/d6qo00325g

Jaime Tostado, Alex Hipólito, Jaime Mateos-Gil, Raúl Losantos, Diego Sampedro, Manuel A. Fernández-Rodríguez

{"title":"Synthesis of fluorescent cyclopentene-fused-phenanthrenes via boron trifluoride-promoted cascade cationic cyclization","authors":"Jaime Tostado, Alex Hipólito, Jaime Mateos-Gil, Raúl Losantos, Diego Sampedro, Manuel A. Fernández-Rodríguez","doi":"10.1039/d6qo00325g","DOIUrl":"10.1039/d6qo00325g","url":null,"abstract":"<div><div>A metal-free, BF<sub>3</sub>-promoted cascade cyclization of biaryl-embedded enynones with nitriles is disclosed, enabling rapid access to amide-functionalized cyclopentene-fused phenanthrenes under mild conditions. The transformation is initiated by electrophilic activation of the enone, which triggers two consecutive intramolecular cyclizations followed by a Ritter-type reaction. This process builds two new C–C bonds, one C–N bond, and one CO bond, affording structurally intricate tetracyclic frameworks with high efficiency. In contrast to previously reported related cyclizations, this strategy uniquely exploits both electrophilic sites of the enone and incorporates external nucleophiles beyond water, thereby substantially expanding the synthetic scope of enynone-based cationic cascade processes. The protocol exhibits broad applicability to enynone substrates and accommodates a diverse array of nitriles, underscoring its synthetic versatility. Mechanistic studies, supported by DFT calculations and experimental evidence, elucidate the origins of reactivity and selectivity. Notably, the resulting polycyclic products display remarkable photophysical properties, with solid-state fluorescence quantum yields of up to 0.35, highlighting their potential as fluorescent materials and molecular probes.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 13","pages":"Pages 3952-3959"},"PeriodicalIF":0.0,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148503365","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}

引用次数: 0