Organic Chemistry Frontiers最新文献

{"title":"Beyond HAT: Harnessing TBADT for photocatalyzed Giese-type C(sp3)-C(sp3) Bond Formation through Reductive Decarboxylation","authors":"Matteo Leone, Dalila Arnaldi, Maurizio Fagnoni","doi":"10.1039/d5qo00399g","DOIUrl":"https://doi.org/10.1039/d5qo00399g","url":null,"abstract":"Photocatalysis has become a powerful tool for developing sustainable synthetic methods, with the decatungstate anion (TBADT) playing a pivotal role. TBADT facilitates a variety of chemical transformations under mild conditions, primarily through hydrogen atom transfer (HAT) and marginally through single electron transfer (SET) mechanisms. This study explores the dual ability of TBADT to cleave C-H bonds and initiate SET processes, leading to efficient C(sp3)-C(sp3) coupling reactions. We address the main limitations of direct HAT by leveraging the bi-reduced form of TBADT [W10O32]6− to activate redox-active esters (RAEs), enabling the formation of alkyl radicals for Giese-type additions. An extensive screening of various hydrogen donors showed their pivotal role in the selective generation of the reduced form of TBADT and in suppressing any undesired C-H activation. Our optimized conditions, using γ-terpinene as the hydrogen donor, achieved high yields in alkylations of various olefins, demonstrating the versatility and robustness of the proposed strategy. This methodology extends the application of TBADT in sustainable organic synthesis and in late-stage functionalization of complex molecules for the synthesis of pharmaceutical building blocks.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"55 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-05-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143903008","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":"Mechanistic insights into ligand-controlled diastereoselectivity in iridium-catalyzed stereoselective coupling of allylic ethers and alkynes: a DFT perspective","authors":"Manzhu Zhao, Lihan Zhu, Qian Zhang, Jingping Zhang","doi":"10.1039/d5qo00343a","DOIUrl":"https://doi.org/10.1039/d5qo00343a","url":null,"abstract":"Regulating the diastereoselectivity of a reaction is highly attractive but extremely challenging, density functional theory computations are employed to investigate an iridium-catalyzed ligand-controlled diastereoselectivity switch propargylic C−H functionalization. Energetically most preferred pathway is found to proceed through (a) BF3-assisted abstraction of methoxide, (b) proton transferred from the tetramethylpiperidine (TMPH) to the unsaturated bond of dienes, and (c) C−C bond formation between propargyl and allyl moiety to furnish the synthetically versatile 1,5-enyne products. The MeOBF3− generated in situ generation is found to remain associated between the ligand and incoming substrates as a counterion, and plays a key role in controlling the diastereoselectivity in the enantiocontrolled (as well as the turn-over determining step) nucleophilic addition. All two stereoisomers of the product bearing two contiguous stereogenic centers could be accessed by changing the chirality of ligands, the chiral induction was found to depend on the synergy that exists among chiral portion of the phosphoramidites and the counterion MeOBF3−. Due to the ligand chirality changes in the catalytic microenvironment, the noncovalent interactions (NCIs) is differentiated between the chiral cavity and the counterion in the diastereoselective transition states, therefore, the efficient and selective conversion is achieved. Therefore, a counterion-ligand cooperative induced stereocontrol approach is proposed, the corresponding NCIs in stereocontrolling transition states are found to be the differentiating factors rendering the stereochemically distinct transition states to be the lowest energy one. This study not only provides a deep mechanistic understanding of the diastereoselectivity propargylic C−H functionalization but also establishes a novel counterion-ligand cooperative strategy for precise stereocontrol, offering a versatile and efficient approach for the synthesis of complex chiral molecules in asymmetric catalysis.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"16 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-05-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143901779","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":"Tetraphenylethylene or Naphthalimide-Functionalized Dendritic Carbazole AIEgens: Self-Assembly Visualization, Three Disparate Force-Triggered Fluorescence Responses, and Advanced Anticounterfeiting Applications","authors":"Yijie Zou, Zhao Chen, Fei Zhao, Ya Yin, Kaixin He, Xingru Liang, Haifeng He, Zhijian Li, Shenghua Liu","doi":"10.1039/d5qo00393h","DOIUrl":"https://doi.org/10.1039/d5qo00393h","url":null,"abstract":"Three 1,8-naphthalimide-modified donor-π-acceptor type and three tetraphenylethylene-functionalized fluorogenic dendritic carbazole derivatives are designed and synthesized. These six dendrimer-like carbazole-containing compounds are typical aggregation-induced emission (AIE) luminogens. Specially, the AIE-active 3CzB2Nap possessing trimeric carbazole and two 1,8-naphthalimide groups is featured by aggregation-triggered self-assembly, and the visualization of its intriguing self-assembly process is successfully realized through scanning electron microscopy technology. Notably, three types of contrasting anisotropic mechanical force-induced fluorescence responses from the six prepared dendritic carbazole AIEgens are observed. More specifically, 7CzB2TPE and 3CzB2Nap do not exhibit fluorescence changes after grinding; 1CzB2TPE and 3CzB2TPE display irreversible mechanofluorochromic phenomena; 1CzB2Nap and 7CzB2Nap show reversible mechanofluorochromic characteristics. To deeply elucidate their three distinct types of force-responsive emissive features of six dendritic AIEgens, powder and single-crystal X-ray diffraction, differential scanning calorimetry experiments, and theoretical simulation calculations of molecular packing structures before and after grinding are carried out. Based on the observed three disparate force-dependent fluorescence phenomena, two advanced information security systems involving multilevel painting anticounterfeit and multimode information encryption are elaborately constructed.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"19 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143885181","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":"Enantioselective construction of cycloalkyl amines via nickel-catalysed alkene desymmetrization","authors":"Ludi Li, Bo Chen, Wenxu Cao, G. V. Surendra Babu, Weike Liao, Pengli Zhang, Guoqin Xia","doi":"10.1039/d5qo00590f","DOIUrl":"https://doi.org/10.1039/d5qo00590f","url":null,"abstract":"Three-dimensional chiral cyclic frameworks containing multiple stereocenters are prevalent skeletons in natural products and bioactive molecules. Nevertheless, the synthetic methods for these architectures are limited to date. In this study, an efficient synthetic route for cyclic chiral amines with two adjacent stereocenters was developed by employing symmetric cyclopentenylamine derivatives as starting materials. This reaction demonstrates a broad substrate scope with various functional groups, resulting in excellent yields and stereoselectivities.The proposed mechanism involves a sophisticated sequence of NiH species-mediated transformations, including NiH insertion, -hydride elimination, reversed NiH insertion and alkylation steps, which collectively enable the precise construction of these complex chiral architectures.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"222 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143885180","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 aryl ortho-C–H thiolation of aldehydes via a transient directing group strategy","authors":"Mingshun Mei, Dongsheng Yi, Fanyi Meng, Junhao Tang, Yanghui Zhang","doi":"10.1039/d5qo00472a","DOIUrl":"https://doi.org/10.1039/d5qo00472a","url":null,"abstract":"Transition metal-catalyzed C–H functionalization represents a robust method for the synthesis of aryl sulfides. The current reactions primarily rely on the use of preinstalled directing groups, which limits their practical applications. Herein, we report the first example of transient directing group-enabled C–H thiolation. Using an aminobenzoic acid as catalyst, aryl aldehydes form the transient imine directing groups and undergo copper-catalyzed aryl <em>ortho</em>-C–H thiolation. The reactions feature a broad substrate scope, facilitating easy access to a diverse range of aryl sulfides. Furthermore, the synthetic utilities of these reactions have been demonstrated by their applications to key intermdediates relevant to the synthesis of drug and bioactive molecule.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"81 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143885182","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":"Synthesis of 8-membered trifluoromethyl benzoxazocines via a Pd-catalyzed ring-expansion reaction of trifluoromethyl benzoxazinones with 2-methylidenetrimethylene carbonate and mechanistic investigations","authors":"Bo Yang, Peng-Fei Sun, Xue Ma, Zhouyang Long, Li-Ming Zhao","doi":"10.1039/d4qo02076f","DOIUrl":"https://doi.org/10.1039/d4qo02076f","url":null,"abstract":"We report a Pd-catalyzed ring-expansion reaction of trifluoromethyl benzoxazinones with 2-methylidenetrimethylene carbonate. This method exhibits high efficiency and broad functional group tolerance, which leads to the rapid assembly of a series of valuable 8-membered trifluoromethyl benzoxazocines with good yields in a simple manner. The synthetic utility of the approach is demonstrated by the facile transformation of product. Finally, the reaction mechanism was investigated by density functional theory (DFT) calculations, suggesting that the carbonyl group has a greater influence on the site-selectivity than the trifluoromethyl group in the decarboxylative ring re-construction process of benzoxazinones.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"17 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143880874","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":"Multicomponent Synthesis of Unsymmetrical 1,2-Diamines via Photo-Induced Carbonyl Alkylative Amination","authors":"Zhuohua Li, Wenjie Yan, Xiao Zhou, Chao Yang, Lin Guo, Wujiong Xia","doi":"10.1039/d5qo00479a","DOIUrl":"https://doi.org/10.1039/d5qo00479a","url":null,"abstract":"Vicinal diamines (or 1,2-diamines) are privileged structural motifs present in many bioactive molecules and drug candidates. The past few decades have witnessed substantial progress on the synthesis of unsymmetrical 1,2-diamines via several strategies, including olefin diamination, α-amino carbanion- or radical-mediated Mannich reaction. However, methods for the one-step preparation of valuable N,N’-dialkylated 1,2-diamines are still rarely reported. We report herein a photo-induced carbonyl alkylative amination reaction that, for the first time, brings together amines, aldehydes, and iodoarenes under catalyst- and base-free conditions for the synthesis of diverse alkyl/aryl-substituted unsymmetrical 1,2-diamines. This method shows broad scope and good tolerance of functional groups. Furthermore, detailed mechanistic investigations reveal that the reaction proceeds via visible light-mediated radical chain process.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"17 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143880875","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":"Enantioselective and Diastereodivergent Construction of Oxindole-pyrazolone Conjugates Bearing an Alkenyl Substituted Quaternary Chlorinated Stereogenic Centre","authors":"Jiapei Chen, Xusheng Duan, Mengyuan Wu, Guishun Bai, Jian-Wei Chen, Xuanrong Sun, Jean Rodriguez, Damien Bonne, Hong Wang, Xiaoze Bao","doi":"10.1039/d5qo00499c","DOIUrl":"https://doi.org/10.1039/d5qo00499c","url":null,"abstract":"Chlorinated stereogenic carbon centres are important elements both in pharmaceutical reagents and synthetic intermediates. Herein, a novel methodology was reported for the construction of rarely developed alkenyl substituted quaternary chlorinated stereogenic centre, featuring oxindole and pyrazolone pharmacophores. Remarkably, the configuration of the double bond was switchable via the combination of suitable base and solvent. In addition, the enantioselective synthesis of the <em>Z</em>-type products was achieved with natural quinidine as catalyst, affording the chlorinated products in excellent yields and stereoselectivities. Preliminary <small>¹</small>H-NMR titration was studied to give insights into the control of the double bond’s configuration. Moreover, the anti-tumour activity against A549 cell-line of these newly synthesized chemical entities was evaluated, and the product (<em>E</em>)-<strong>5ca</strong> was revealed as promising anti-tumour reagent.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"44 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143885183","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":"Regioselective C-H Alkynylation with Haloalkynes Enabled by Nitrogen Functionality","authors":"Qiaoya Zhang, Bifu Liu, Ci Chen, Yinling Li, Kejun Feng, Sheng Hu, Yang Gao, Yanping Huo, Qian Chen, Xianwei Li","doi":"10.1039/d5qo00578g","DOIUrl":"https://doi.org/10.1039/d5qo00578g","url":null,"abstract":"Regioselective introduction of versatile alkyne functionality would enable rapid construction of molecular complexity, however, steric hindered silyl-contained alkynylation reagents were typically required, and thus, hampered the further applications. Herein, we developed transformable nitrogen functionality enabled regioselective C‒H alkynylation cascade with aliphatic haloalkynes, furnishing alkynes and heterocycles, which thus facilitated concise delivery of CB2 receptor agonist, protein kinase inhibitor analogues.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"4 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143875842","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":"1,2 Wagner-Meerwein Shift in Aza-Nazarov Cyclization: Bi(III)-Catalyzed Substrate-Dependent Divergent Synthesis of Highly Substituted Pyrroles and Indenes","authors":"Deepak Datta Gaonkar, Shon Gangai, Krishna Appasaheb Mhaske, Rishikesh Narayan","doi":"10.1039/d5qo00168d","DOIUrl":"https://doi.org/10.1039/d5qo00168d","url":null,"abstract":"Nazarov reaction and its variants such as Aza-Nazarov and Iso-Nazarov cyclizations are versatile methods for the synthesis of five-membered ring systems including pyrroles and indenes. 1,2-Wagner Meerwein shift has been combined in a domino sequence with both Nazarov and Aza-Nazarov-like reactions for the synthesis of cyclopentenone and indole derivatives respectively. However, the same sequence has not been applied for the synthesis of pyrroles, possibly due to the high reactivity of 1-azapentadienyl cation intermediates. In this report, we present the first example of an Aza-Nazarov/1,2-Wagner Meerwein shift domino sequence for the synthesis of highly substituted pyrroles. The use of Bi(III) as a mild main group metal catalyst was found to be crucial to control the high reactivity of the intermediate. The substrate demonstrated substituent-dependent divergence in product formation to selectively give indenes through iso-Nazarov cyclization, besides pyrroles. Detailed mechanistic investigations reveal electrocyclization nature of the reaction involving a cationic intermediate generated under Lewis and/or ‘Hidden Brǿnsted acid’ catalysis conditions.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"16 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143876085","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}