Journal of Organic Chemistry最新文献

{"title":"Excellence in Industrial Organic Synthesis 2024","authors":"Bernd Schaefer, Shashank Shekhar, James Murray","doi":"10.1021/acs.joc.5c00303","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00303","url":null,"abstract":"Published as part of <i>The Journal of Organic Chemistry</i> special issue “Excellence in Industrial Organic Synthesis 2024”. In the chemical industry, alongside the discovery of new substances and their properties, the development and optimization of chemical reactions and processes play a decisive role, not least for economic reasons. (1,2) This is nothing new. The interplay between research and development, and thus the pursuit of excellence in chemistry, has characterized the industry from the very beginning and will certainly continue to make a decisive contribution in the future, mastering the major challenges we are currently facing, from the demand for increased sustainability and efficient CO<sub>2</sub> management to the changes in the supply of raw materials and energy. The conceptual foundations of excellence in chemistry can be traced back to the principle of parsimony by William of Ockham (1286–1347), a medieval Franciscan monk, and on his proverbial razor, in which he summed up the motivation of optimization in a single sentence: “It is futile to do with more what can be done with fewer” (Lat.: “<i>Frustra fit per plura, quod potest fieri per pauciora</i>”). (3,4) In accordance with this concept, James B. Hendrickson (1928–2018) outlined his ideas on the logic of organic chemistry and <i>ideal synthesis</i> already in 1975. (5,6) Barry Trost’s thoughts on <i>atom economy</i> followed in the early 1990s, while Paul A. Wender came up with function-oriented synthesis and <i>step economy</i> in 2008 (7) and Phil Baran and Reinhard Hoffmann with <i>redox economy</i> at almost the same time. (8) In parallel, Roger A. Sheldon emphasized the need for a new paradigm in the evaluation of efficiency in chemical production, assigning value not only to chemical yield but also to waste minimization. By developing the E-factor concept, which is now used throughout the industry in one form or another, he brought <i>elegance and precision</i> to large-scale production. (9−11) In this respect, it is perhaps not too surprising that some of these elegant processes have already been in operation for a while. As examples one may consider Evonik’s methionine production, BASF’s citral synthesis, and Rhodia’s vanillin process. (12) Taking James Hendrickson’s thoughts on the <i>ideal synthesis</i> as a starting point, this year we can indeed celebrate 50 years of excellence in industrial organic synthesis. Articles included in this Special Issue cover a wide variety of research topics such as discussion on strategies for kilogram-scale synthesis with emphasis on safety, robustness, and sustainability, flow and impinging-jet technologies, new catalytic methods, integration of Process Analytical Technologies (PAT) for solid-phase peptide synthesis, and green chemistry to name a few. These outstanding contributions provide an exquisite overview of the current state of the art and certainly pave the way for further improvements. Consistent with earlier issues i","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846673","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":"Excellence in Industrial Organic Synthesis 2024","authors":"Bernd Schaefer*, Shashank Shekhar* and James Murray*, ","doi":"10.1021/acs.joc.5c0030310.1021/acs.joc.5c00303","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00303https://doi.org/10.1021/acs.joc.5c00303","url":null,"abstract":"","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 15","pages":"5081–5082 5081–5082"},"PeriodicalIF":3.3,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143842231","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":"Late-Stage Functionalization Strategies of 1,2,3-Triazoles: A Post-Click Approach in Organic Synthesis","authors":"Mangal S. Yadav, Vinay K. Pandey, Manoj K. Jaiswal, Sumit K. Singh, Anindra Sharma, Mayank Singh, Vinod K. Tiwari","doi":"10.1021/acs.joc.5c00125","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00125","url":null,"abstract":"The 1,2,3-triazole scaffolds are an important class of biologically privileged heterocyclic compounds with several key applications in chemistry, biology, medicine, agriculture, and material science. The “postclick” functionalization of 1,2,3-triazoles may emerge as a promising tactic for the construction of molecular architectures of therapeutics and is considered to be a growing area of investigation. This interest extends beyond the regioselective Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) method that involves the trapping of Cu(I)-triazole with suitable precursors. In this Perspective, we highlight the growing impact of postclick strategies in organic synthesis required for the late-stage functionalization of 1,2,3-triazoles with a hope that this emerging concept may provide ample opportunities in modern organic synthesis of notable applications in medicinal chemistry, biology, and materials science.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"28 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143849705","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":"Rapid and Additive-Free Synthesis of β-Sulfido Sulfonyl Fluorides through N-Methyl-2-pyrrolidinone (NMP)-Promoted Thia-Michael Addition","authors":"Junwei Han, Qiushuo Zheng, Xin Ding, Yuqin Wen, Nengrong Chen, Wanzhen Lin, Fa-Jie Chen","doi":"10.1021/acs.joc.5c00025","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00025","url":null,"abstract":"β-Sulfido sulfonyl fluorides, incorporating a clickable sulfonyl fluoride and a thioether motif, are valuable intermediates in chemical biology, materials science, and drug discovery. Herein, we developed a rapid and additive-free synthesis of these compounds via <i>N</i>-methyl-2-pyrrolidinone (NMP)-promoted thia-Michael addition of thiols to ethene sulfonyl fluoride (ESF). The reaction proceeds smoothly under neutral conditions without the need for a base or catalyst, achieving high efficiency within 20 min. This method demonstrates a broad substrate scope, tolerating thiophenols, alkylthiols, thioglycosides, and cysteine-containing peptides. The resulting β-sulfido sulfonyl fluorides enable diverse transformations, such as sulfur(VI) fluoride exchange (SuFEx) reaction and thioether oxidation, facilitating applications in drug conjugates and materials, such as additives for lithium-ion battery electrolyte components.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"75 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846675","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":"Asymmetric and Symmetric S-zig-zag-Fused BODIPYs: Synthesis and Photophysical and Oxidative Properties","authors":"Ruihan Yang, Lu Li, Shulin Gao, Zhehui Weng, WeiLi Li, Zhaohui Wang, Xiangguang Li, Yanhua Yang, Wei Jiang","doi":"10.1021/acs.joc.5c00508","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00508","url":null,"abstract":"We present a new, straightforward, and versatile approach that utilizes regioselective brominated precursors to synthesize both asymmetric and symmetric S-<i>zig-zag</i>-fused BODIPYs (<b>s-TFB</b> and <b>bis-TFB</b>) in moderate yields (45% and 40%, respectively). X-ray structure analyses reveal that the planar rigidity of the BODIPY skeleton is progressively enhanced with an increasing number of thiopyran rings. The annulation of S-heteroaromatic rings at the <i>zig-zag</i> edge of the BODIPY core results in blue-shifted absorption and emission spectra, with <b>bis-TFB</b> exhibiting maxima at 530 and 539 nm and elevated LUMO energy levels. In contrast, oxidation of <b>s-TFB</b> and <b>bis-TFB</b> with <i>m</i>-CPBA demonstrates significant site selectivity, affording four oxidation products, namely <b>s-s-SFB</b>, <b>s-bis-SFB</b>, <b>bis-s-SFB</b>, and <b>bis-bis-SFB</b>, in yields ranging from 22% to 36%. These oxidated S-<i>zig-zag</i>-fused BODIPY derivatives display large red-shifted absorption and emission spectra (e.g., 648 and 735 nm for <b>s-bis-SFB</b>), along with more stable HOMO and LUMO energy levels and reduced HOMO–LUMO gaps. This S-<i>zig-zag</i>-fused cyclization/oxidation strategy enables precise tuning of the BODIPY optoelectronic properties, opening new avenues in dye design and application.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"24 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143849707","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":"Rational Design of Supramolecular Receptors for Consistent Binding Affinities under High-Salinity Conditions","authors":"Borja Gómez-González, Nuno Basílio, Belén Vaz, M. Rita Paleo, F. Javier Sardina, Moisés Pérez-Lorenzo, Luis García-Río","doi":"10.1021/acs.joc.5c00068","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00068","url":null,"abstract":"The development of water-soluble multicharged macrocycles has opened promising pathways in biomedical applications, enabling selective molecular recognition for therapeutic and diagnostic uses. Yet, traditional polyanionic and polycationic receptors often face performance limitations under realistic operating conditions. A major drawback is the natural tendency of these polycharged hosts to experience increasing screening effects as concentration rises due to self-ion pairing phenomena, which can reduce binding efficiency by several orders of magnitude. These issues are further intensified when polyionic receptors are used in high-salinity environments, typically used to replicate physiological settings, where the abundance of ions introduces additional screening effects that diminish the supramolecular affinity for a wide range of guests. This study presents a new approach that leverages zwitterionic synthetic receptors with rationally engineered architectures to overcome these challenges. By incorporation of specific structural features, self-ion pairing is eliminated, effectively making host concentration no longer a controlling factor in the thermodynamics of the complexation process. Additionally, these dual-charged hosts achieve self-contained stabilization, naturally shielding recognition sites from external ion interference under high-salinity conditions. Furthermore, the ability of these supramolecular hosts to encapsulate zwitterionic guests, a challenging task due to the strong solvation of these molecules in aqueous solution, adds significant value to the functional versatility of these macrocycles. Altogether, these findings represent a significant advancement in the design of stable and adaptable receptor systems for complex environments.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"38 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143842146","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":"Inherently Chiral Seven- and Eight-Membered Rings: Enantioselective Synthesis and Applications","authors":"Yu Luo, Shuang Luo, Qiang Zhu","doi":"10.1021/acs.joc.5c00479","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00479","url":null,"abstract":"Compared to smaller or larger rings, seven- and eight-membered carbo- and heterocycles are typically nonplanar and exhibit greater conformational rigidity. This property alone can impart chirality to certain 7- or 8-membered ring systems. Herein, we summarize recent achievements in the enantioselective synthesis of this class of inherently chiral medium rings, including both ring construction and ring modification, as well as the applications of chiral ligands and catalysts derived from these rigid cyclic scaffolds in asymmetric catalysis.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"3 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841984","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":"Scandium Triflate Catalyzed Cycloadditions of Vinyl Diazo Compounds and In Situ Formed Naphthoquinone Methides","authors":"Yi-Xiao Yin, Jie Zhan, Ren Liu, Pran Gopal Karmaker, Qing Zhou, Wen-Dao Chu, Quan-Zhong Liu","doi":"10.1021/acs.joc.5c00425","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00425","url":null,"abstract":"Vinyl diazo carbonyl compounds have received great attention and are widely employed in the cycloadditions of in situ formed reactive intermediates. Metal carbenes are predominantly involved in cycloadditions, and transformations of vinyl diazo compounds that do not proceed via the metal carbene pathway have been seldom reported. Herein, scandium-catalyzed cycloadditions of vinyl diazo compounds and in situ formed 2-naphthoquinone-8-methides are achieved, and naphthalene-fused polycyclic products were obtained in up to 88% yield. In the transformation, the nucleophilic conjugate addition of vinyl diazo compounds to in situ formed 2-naphthoquinone-8-methides generates vinyl diazonium intermediates, which undergo an intramolecular Friedel–Crafts reaction and intramolecular transesterification to yield the final product.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"9 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841988","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":"Synthetic Studies toward the Total Synthesis of Scabrolide A","authors":"Sabnam Begum, Tushar Kanti Chakraborty","doi":"10.1021/acs.joc.5c00298","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00298","url":null,"abstract":"Herein, we report a concise route to the [5-5-6]-fused tricyclic core of scabrolide A and our efforts toward the construction of the fourth cycloheptane ring of the molecule via a 7-<i>endo-trig</i> radical cyclization. The tricyclic cyclohexenone core was assembled by a ring-closing metathesis (RCM) reaction followed by oxidation and concomitant isomerization of the double bond. These promising results have potential implications in the synthesis of similar tricyclic cores of many other congeners within this family of furanobutenolide-derived polycyclic cembranoids and norcembranoids.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"24 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143836905","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":"Merging Electrosynthesis and Biocatalysis to Access Sulfur-Based Chiral α-Fluorinated Carboxylic Acids","authors":"Parmjeet Kaur, Vikas Tyagi","doi":"10.1021/acs.joc.4c03019","DOIUrl":"https://doi.org/10.1021/acs.joc.4c03019","url":null,"abstract":"We describe a sustainable process to synthesize chiral sulfur-based organofluorine compounds by integrating electrosynthesis and biocatalysis within a single vessel while using water as a solvent. In this context, differently substituted 2-fluoro-3-mercaptopropionic acids have been synthesized in good isolated yields using thiophenols and fluorine-containing α,β-unsaturated alkenes. In addition, molecular docking and control experiments were carried out that suggest the formation of radical species during the electrolysis and participation of the lipase active site during the biocatalysis. The scalability and applicability of the developed protocol have been illustrated through the synthesis of a key intermediate of the MMP-3 inhibitor and by performing a gram-scale reaction. Further, the compatibility of the lipase enzyme with electricity highlights the promising potential of enzymatic electrosynthesis in advancing environmentally friendly organic transformations.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"28 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841985","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}