Organic Chemistry Frontiers最新文献

{"title":"Outstanding Reviewers for Organic Chemistry Frontiers in 2024","authors":"","doi":"10.1039/d5qo90049b","DOIUrl":"https://doi.org/10.1039/d5qo90049b","url":null,"abstract":"We would like to take this opportunity to thank all of <em>Organic Chemistry Frontiers</em>’ reviewers for helping to preserve quality and integrity in chemical science literature. We would also like to highlight the Outstanding Reviewers for <em>Organic Chemistry Frontiers</em> in 2024.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"11 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144547466","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"DNA-Compatible Synthesis of Amidine Pharmacophores via Late-Stage Amine Modification","authors":"Huihong Wang, Jiale Huang, Xianfu Fang, Huilin Liao, Gong Zhang, Wei Fang, Yizhou Li","doi":"10.1039/d5qo00818b","DOIUrl":"https://doi.org/10.1039/d5qo00818b","url":null,"abstract":"Amidines are prevalent pharmacophores that are widely utilized in medicinal chemistry. The selective modification of amines within DNA-encoded libraries (DELs) offers a direct approach to constructing these pharmacophores, thereby enhancing library structural diversity. Herein, we report a hydroxylamine-mediated conversion of amino groups to amidines, based on our ongoing development of in situ conversion strategies. This method enables efficient coupling with diverse nitriles and demonstrates broad tolerance to protecting groups. Furthermore, we successfully applied this approach to the on-DNA synthesis of iNOS and PAD4 inhibitors.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"23 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144547467","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrochemical Synthesis of Phosphorylated Glycine-Containing Oligopeptides","authors":"Jian Wang, You Huang, Yirui Shen, Fulai Li, Yufen Zhao, Ju Wu","doi":"10.1039/d5qo00803d","DOIUrl":"https://doi.org/10.1039/d5qo00803d","url":null,"abstract":"DABCO-mediated electrochemical synthesis of phosphorylated Glycine-containing oligopeptides has been developed, which eliminates the need for external oxidants. A series of di/tri/tetra/pentapeptides with different amino acid sequences were obtained in moderate to good yields under mild conditions. Remarkably, the synthetic applicability was further demonstrated through its easy scalability, and the in vitro cytotoxicity against HeLa, MDA-MB-231, HCT116 cells of the phosphorylated peptides was investigated.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"19 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144547469","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Elucidating the mechanism and origin of stereoselectivity in C-C bond formation under isothiourea and amine cooperative catalysis","authors":"Hui-Juan Liu, Yang Wang","doi":"10.1039/d5qo00726g","DOIUrl":"https://doi.org/10.1039/d5qo00726g","url":null,"abstract":"Cooperative catalysis integrating chiral amine and isothiourea organocatalysts offers a promising yet underexplored strategy for stereodivergent C–C bond formation. However, the interplay of their orthogonal activation modes and the origins of stereoselectivity remain poorly understood. This study deciphers the cooperative interplay of chiral amine and isothiourea catalysts in stereodivergent Michael additions through DFT analysis. Activation of the α,β-unsaturated aldehyde forms an iminium intermediate and activation of an ester forms an ammonium enolate. Notably, the in situ generated C6F5OH plays a key role in facilitating dehydrolysis to form the iminium intermediate. Noncovalent interaction and AIM analyses demonstrate that Si-Re addition pathway dominates due to stabilizing noncovalent interactions (i.e., C-H···π and π···π interactions), favoring the RS-configured product. Furthermore, the FMO analysis identify that the implication of an amine with α,β-unsaturated aldehyde can largely lower the energy barrier of C-C bond formation step by lowering the LUMO energy of α,β-unsaturated aldehyde.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"11 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144533710","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Photocatalytic Cleavage of Unactivated C(sp3)-H Bonds via Uranyl Cation: Enabling Allylation of Alkanes","authors":"Yanxin Jiang, Songbai Tang, Yinying Luo, Zi-Xin Wang, Ze-Kai Li, Jing Su","doi":"10.1039/d5qo00649j","DOIUrl":"https://doi.org/10.1039/d5qo00649j","url":null,"abstract":"The direct allylation of C-H bonds is a highly efficient and environmentally friendly method. Herein, a suc-cessful allylation of C(sp3)-H bond using uranyl cation as a highly efficient direct H atom transfer (d-HAT) agent is reported. Excellent substrate scopes were demonstrated. Scale-up experiments and continuous-flow experiment showed the application prospects. The proposed mechanism was verified through Stern-Volmer fluorescence quenching experiments, HR-MS analysis, kinetic isotope effect (KIE) studies, and light on/off experiments. Furthermore, this method demonstrates considerable potential for introducing various higher-value functional groups, including carboxyl, ester, cyano, and dialkyl substitutions, highlighting its synthetic utility in chemistry.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"54 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144533715","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Copper-Catalyzed Stereo-Controllable Silylation of Allylic gem-Dichlorides","authors":"Zi-Lu Wang, Pan-Pan Tian, Yun-He Xu","doi":"10.1039/d5qo00690b","DOIUrl":"https://doi.org/10.1039/d5qo00690b","url":null,"abstract":"Herein, we present a ligand-regulated, stereo-controllable silylation reaction of allylic gem-dichlorides. In the absence of ligand, the reaction yields (Z)-vinyl chlorides with high stereoselectivity. Conversely, using a chiral Pybox ligand leads to the formation of (E)-vinyl chlorides with high enantioselectivity. This method demonstrates broad substrate compatibility, effectively producing the desired (Z)- and (E)-vinyl chloride products from a variety of aliphatic and aromatic allylic gem-dichlorides.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"39 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144533712","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Photoredox catalytic γ‑C(sp3)−H vinylation of hydroxamic acid derivatives via 1,5-hydrogen-atom-transfer-mediated cross-dehydrogenative coupling","authors":"Lingli Liu, Yangjian Cheng, Changduo Pan, Jin-Tao Yu","doi":"10.1039/d5qo00747j","DOIUrl":"https://doi.org/10.1039/d5qo00747j","url":null,"abstract":"A visible-light-induced regioselective γ-C(sp3)-H vinylation of hydroxamic acid derivatives with 2-aryl enamides was developed via cross-dehydrogenative coupling (CDC) reactions for the first time. This remote γ-vinylation was realized by the 1,5-hydrogen atom transfer (1,5-HAT) of the amidyl radicals that in situ generated through the potocatalytic N-O bond cleavage of hydroxamic acid derivatives.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"36 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144520994","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Three-component copper-catalyzed difluoroalkylamidation of alkynes: An efficient approach to difluoroalkylated enamides","authors":"Jing Ren, Kaiyun Liu, Jinlong Li, Xinyu Long, Kaizhi Li","doi":"10.1039/d5qo00751h","DOIUrl":"https://doi.org/10.1039/d5qo00751h","url":null,"abstract":"This paper describes a selective three-component 1,2-difluoroalkylamidation of alkynes enabled by a coordinating activation strategy. This protocol utilizes commercially available difluoroalkyl halides as radical precursors and picolinamides as nitrogen sources, facilitating the synthesis of difluoroalkylated enamides with broad substrate scope, good functional group compatibility, and exceptional stereoselectivity. The modular catalytic synthesis is characterized by its ease of implementation, broad molecular diversity, and flexibility in late-stage modifications.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"14 10 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144520791","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Benzylic C–H bond functionalization through photo-mediated mesyloxy radical formation","authors":"Jola Pospech, Jannik Thaens, Xinzhe Shi, Tobias Taeufer, Janina Schlapp","doi":"10.1039/d5qo00683j","DOIUrl":"https://doi.org/10.1039/d5qo00683j","url":null,"abstract":"Herein, we report a photo-mediated methodology for the benzylic C‒H bond oxygenation. Our approach employs in-situ generated (methylsulfonyloxy)-pyridinium mesylate salts to produce mesyloxy radicals apt for benzylic C‒H bond cleavage through hydrogen atom transfer (HAT). Subsequent oxidation of the benzylic radical yields a carbocation, functionalized by the mesylate counterion through oxidative radical-polar crossover (ORPC). The reactive benzylic mesylates are converted to stable benzylic alcohols via a straightforward protocol. Reaction optimization utilized modern design of experiment techniques (DoE) for facile setup and rapid reaction. Our proposed mechanistic paradigm is supported by comprehensive investigations, including fluorescence quenching studies, cyclic voltametric measurements, and determination of kinetic isotope effects (KIE). Density functional theory (DFT) calculations elucidate the divergent performance between (methylsulfonyloxy)-pyridinium salts and (trifluoromethylsulfonyloxy)-pyridinium salts. The functionalization of unactivated C–H bonds represents a versatile strategy for the diversification of drug intermediates in synthetic organic chemistry.1, 2 Besides transition metal catalysis, electrosynthesis or biocatalysis, the utilization of radical-species for C–H bond functionalization has been rapidly gaining attention.3-8 In the past, radicals were frequently generated under harsh reaction conditions, restricting compatibility with functional groups. However, the advent of photoredox catalysis has facilitated the generation of radicals under mild conditions.9,10 In this context, redox-active pyridinium salts have served as unique radical precursors, generating reactive species after single-electron reduction by an appropriate photoredox catalyst.11-15 Electronic effects have a significant impact on the generation and reactivity of radical species.16 For instance, the electronic properties of both the exocyclic and heteroarene substituents in redox-active pyridinium salts play a crucial role in dictating the formation of N-centered versus X-centered radicals through dissociative electron transfer (DET) (Figure 1).17 Strongly electron withdrawing N-substituents X (e.g. TfO‒ and F‒) favour heterolytic bond cleavage generating N-centered pyridinium radicals py•+ and less electron-withdrawing N-substituents (e.g. F3CO‒, RO‒) favour homolytic bond-cleavage generating an X-centered radical X•. It has been demonstrated that the resulting radicals can undergo a variety of chemical transformations, which were applied in both C(sp2)‒H and C(sp3)‒H bond functionalisations.18","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"27 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144520988","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Selective deuteration of terminal olefins with D2O by catalysis of osmium-hydride complexes","authors":"Wenwei Qin, Herman H. Y. Sung, Ian D. Williams, Guochen Jia","doi":"10.1039/d5qo00563a","DOIUrl":"https://doi.org/10.1039/d5qo00563a","url":null,"abstract":"An efficient catalytic system for selective deuteration of terminal olefins using D<small>₂</small>O as the deuterium source has been developed. A series of osmium hydride complexes of the type OsHX(CO)(PR<small>₃</small>)<small>₂</small>(L) (where X represents halides) has been evaluated as catalyst precursors for H/D exchange between olefins and D<small>₂</small>O. The catalytic activity of the complexes was found to depend on the ligands present. Among the complexes tested, the OsHI(CO)(PPh<small>₃</small>)<small>₃</small> complex exhibited excellent catalytic activity for the hydrogen–deuterium (H/D) exchange of terminal olefins with D<small>₂</small>O, especially in the presence of acetic acid. The system shows high selectivity for deuteration at terminal double bonds over internal ones. It can catalyze H/D exchange reactions of olefins without causing isomerization and can induce selective H/D exchange at the methine carbon (<img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/><em>C</em>HR) over the methylidene carbon (<img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/><em>C</em>H<small>₂</small>) for substrates RCH<img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/>CH<small>₂</small> with a bulky substituent R. Additionally, these reactions can be performed on substrates with various functional groups, making this system useful for selective labeling of olefins in complex molecules.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"13 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144520989","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}