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Three-Component Synthesis of Oxazolidinones via Phosphine-Catalyzed Fixation of Carbon Dioxide and Mechanistic Investigation in Mass Spectrometry
IF 4.354 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-04-02 DOI: 10.1021/acs.joc.4c03034
Wangyu Li, Shiwen Zhou, He Tang, Fengjian Chu, Hongru Feng, Yuanjiang Pan
A phosphine-catalyzed three-component cyclization reaction between anilines, carbon dioxide, and chloroalkanes was developed for the synthesis of oxazolidinones. This strategy not only proceeds under ambient CO2 pressure and metal-free condition but also shows a broad substrate scope, including aromatic amines, aliphatic amines, chiral amino acid esters, and bioactive molecules, providing an efficient and environmentally benign route to synthesize pharmaceutically relevant N-aryl-oxazolidinones. Mechanistic investigations utilizing mass spectrometry (MS) indicate the involvement of multiple phosphine intermediates in this process, thereby elucidating the underlying mechanism. Moreover, the relationships between these phosphine intermediates and Tolman cone angles or the solvent effect of phosphines were examined through mass spectrometry.
{"title":"Three-Component Synthesis of Oxazolidinones via Phosphine-Catalyzed Fixation of Carbon Dioxide and Mechanistic Investigation in Mass Spectrometry","authors":"Wangyu Li, Shiwen Zhou, He Tang, Fengjian Chu, Hongru Feng, Yuanjiang Pan","doi":"10.1021/acs.joc.4c03034","DOIUrl":"https://doi.org/10.1021/acs.joc.4c03034","url":null,"abstract":"A phosphine-catalyzed three-component cyclization reaction between anilines, carbon dioxide, and chloroalkanes was developed for the synthesis of oxazolidinones. This strategy not only proceeds under ambient CO<sub>2</sub> pressure and metal-free condition but also shows a broad substrate scope, including aromatic amines, aliphatic amines, chiral amino acid esters, and bioactive molecules, providing an efficient and environmentally benign route to synthesize pharmaceutically relevant <i>N</i>-aryl-oxazolidinones. Mechanistic investigations utilizing mass spectrometry (MS) indicate the involvement of multiple phosphine intermediates in this process, thereby elucidating the underlying mechanism. Moreover, the relationships between these phosphine intermediates and Tolman cone angles or the solvent effect of phosphines were examined through mass spectrometry.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"25 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758474","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}
引用次数: 0
Discovery of Zoanthamine Alkaloids from Zoanthus vietnamensis with Antioxidant and Neuroprotective Activities 从具有抗氧化和神经保护活性的越南藻中发现藻胺生物碱
IF 4.354 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-04-02 DOI: 10.1021/acs.joc.5c00280
Shu-Rong Chen, Yang-Chen Chang, Yi Chen, Yih-Fung Chen, Yu-Chi Lin, Cheng-chau Chiu, Yuan-Bin Cheng
Two novel alkaloids, zoanides A and B (1 and 2), 12 new zoanthamine-type alkaloids (314), together with two known compounds (15 and 16) were obtained from the zoantharian Zoanthus vietnamensis. Their structures and absolute configurations were established by extensive spectroscopic data, DP4+ probability calculation, and X-ray crystallographic analyses. Structurally, compound 1 represents an unusual functionalized skeleton caused by oxidative cleavage; compound 2 possesses an unprecedented 6/6/5/6/7-fused pentacyclic carbon skeleton. Additionally, the plausible biosynthetic pathways of 1 and 2 were proposed. All isolates were evaluated in vitro for neuroprotection. Among them, compounds 2, 3, 8, 9, and 15 exhibited neuroprotection against paclitaxel-induced neurite damage without interfering with the anticancer effects of paclitaxel. Moreover, compounds 2 and 9 demonstrated moderate protective effects against oxaliplatin-induced oxidative stress overload without interfering with the anticancer effects of oxaliplatin.
{"title":"Discovery of Zoanthamine Alkaloids from Zoanthus vietnamensis with Antioxidant and Neuroprotective Activities","authors":"Shu-Rong Chen, Yang-Chen Chang, Yi Chen, Yih-Fung Chen, Yu-Chi Lin, Cheng-chau Chiu, Yuan-Bin Cheng","doi":"10.1021/acs.joc.5c00280","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00280","url":null,"abstract":"Two novel alkaloids, zoanides A and B (<b>1</b> and <b>2</b>), 12 new zoanthamine-type alkaloids (<b>3</b>–<b>14</b>), together with two known compounds (<b>15</b> and <b>16</b>) were obtained from the zoantharian <i>Zoanthus vietnamensis</i>. Their structures and absolute configurations were established by extensive spectroscopic data, DP4+ probability calculation, and X-ray crystallographic analyses. Structurally, compound <b>1</b> represents an unusual functionalized skeleton caused by oxidative cleavage; compound <b>2</b> possesses an unprecedented 6/6/5/6/7-fused pentacyclic carbon skeleton. Additionally, the plausible biosynthetic pathways of <b>1</b> and <b>2</b> were proposed. All isolates were evaluated in vitro for neuroprotection. Among them, compounds <b>2</b>, <b>3</b>, <b>8</b>, <b>9</b>, and <b>15</b> exhibited neuroprotection against paclitaxel-induced neurite damage without interfering with the anticancer effects of paclitaxel. Moreover, compounds <b>2</b> and <b>9</b> demonstrated moderate protective effects against oxaliplatin-induced oxidative stress overload without interfering with the anticancer effects of oxaliplatin.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"50 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758475","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}
引用次数: 0
General Chiral Catalysis: A Cinchona Thiourea–Pyridoxazoline Scaffold as Both Organocatalyst and Chiral Ligand for an Enantioselective Mannich Reaction between α-Aminomaleimides and Benzothiazolimines
IF 4.354 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-04-02 DOI: 10.1021/acs.joc.4c02596
Qianmao Zhang, Jingliang Yu, Guo Cheng, Chunchun Tang, Zhenyu Yang, Fang Tian, Lixin Wang
For proof of a new concept of general chiral catalysis, a series of new bifunctional chiral catalysts integrated with both cinchona alkaloid thiourea and pyridine-oxazoline scaffolds were devised and prepared. Using as independent organocatalysts, a new Mannich reaction between α-aminomaleimides and benzothiazolimines with acceptable enantioselectivities (up to 75% ee) has been disclosed. Served as a chiral ligand, the new organocatalyst synergically works with Cu(OTf)2 to catalyze the reaction in excellent enantioselectivities (up to 96% ee) with good yields under mild conditions even in a scale-up preparation. Both the substrates and the final multifunctional chiral adducts may provide a possibility for the development of new pharmaceutical entities and chiral ligands.
{"title":"General Chiral Catalysis: A Cinchona Thiourea–Pyridoxazoline Scaffold as Both Organocatalyst and Chiral Ligand for an Enantioselective Mannich Reaction between α-Aminomaleimides and Benzothiazolimines","authors":"Qianmao Zhang, Jingliang Yu, Guo Cheng, Chunchun Tang, Zhenyu Yang, Fang Tian, Lixin Wang","doi":"10.1021/acs.joc.4c02596","DOIUrl":"https://doi.org/10.1021/acs.joc.4c02596","url":null,"abstract":"For proof of a new concept of general chiral catalysis, a series of new bifunctional chiral catalysts integrated with both cinchona alkaloid thiourea and pyridine-oxazoline scaffolds were devised and prepared. Using as independent organocatalysts, a new Mannich reaction between α-aminomaleimides and benzothiazolimines with acceptable enantioselectivities (up to 75% ee) has been disclosed. Served as a chiral ligand, the new organocatalyst synergically works with Cu(OTf)<sub>2</sub> to catalyze the reaction in excellent enantioselectivities (up to 96% ee) with good yields under mild conditions even in a scale-up preparation. Both the substrates and the final multifunctional chiral adducts may provide a possibility for the development of new pharmaceutical entities and chiral ligands.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"107 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758473","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}
引用次数: 0
Switching Conjugation Is the Predominant Factor Contributing to Complete Reversal of Amide cis–trans (Z-E) Preference through N-Methylation
IF 4.354 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-04-01 DOI: 10.1021/acs.joc.4c02929
Junjun Huang, Luying Chen, Hirotaka Ikeda, Tadashi Hyodo, Yulan Tang, Yuko Otani, Kentaro Yamaguchi, Satoshi Inagaki, Tomohiko Ohwada
N-Methylation strongly influences the cis–trans (Z-E) preference of amides, especially in benzanilide. While the trans (E) conformation is preferred in NH-benzanilide, N-methylation shifts the balance to favor the cis (Z) form. This switch, often attributed to steric hindrance, is frequently utilized in molecular design. However, our findings suggest an alternative mechanism. Through bond model analysis (BMA), we explored the structural preferences driven by bond orbital interactions and assessed the stability of cis–trans (Z-E) preferences in response to electronic perturbations via electron-donating or -withdrawing groups on the benzene rings. Our results reveal that N-methylation rebalances conjugation: NH-benzanilides prefer the trans (E) form due to phenyl-amine conjugation, while N-Me benzanilides favor the cis form due to phenyl-carbonyl conjugation.
{"title":"Switching Conjugation Is the Predominant Factor Contributing to Complete Reversal of Amide cis–trans (Z-E) Preference through N-Methylation","authors":"Junjun Huang, Luying Chen, Hirotaka Ikeda, Tadashi Hyodo, Yulan Tang, Yuko Otani, Kentaro Yamaguchi, Satoshi Inagaki, Tomohiko Ohwada","doi":"10.1021/acs.joc.4c02929","DOIUrl":"https://doi.org/10.1021/acs.joc.4c02929","url":null,"abstract":"<i>N</i>-Methylation strongly influences the <i>cis–trans</i> (Z-E) preference of amides, especially in benzanilide. While the <i>trans</i> (E) conformation is preferred in NH-benzanilide, <i>N</i>-methylation shifts the balance to favor the <i>cis</i> (Z) form. This switch, often attributed to steric hindrance, is frequently utilized in molecular design. However, our findings suggest an alternative mechanism. Through bond model analysis (BMA), we explored the structural preferences driven by bond orbital interactions and assessed the stability of <i>cis–trans</i> (Z-E) preferences in response to electronic perturbations via electron-donating or -withdrawing groups on the benzene rings. Our results reveal that <i>N</i>-methylation rebalances conjugation: NH-benzanilides prefer the <i>trans</i> (E) form due to phenyl-amine conjugation, while N-Me benzanilides favor the <i>cis</i> form due to phenyl-carbonyl conjugation.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"25 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745238","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}
引用次数: 0
Base-Assisted and Silica Gel-Promoted Indole-Substituted Indene Synthesis
IF 4.354 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-04-01 DOI: 10.1021/acs.joc.5c00316
Anurag Verma, Ruchir Kant, Nayan Ghosh
Herein, we report for the first time a transition-metal-free and mild protocol that requires inexpensive K2CO3 and silica gel for direct access to polysubstituted indenes from readily obtainable starting precursors. Notably, sequential Michael addition, intramolecular cyclization, and silica gel-promoted nucleophilic substitution reactions afford the desired products. A broad range of indoles and other aromatic nucleophiles are well-tolerated, affording indenes in moderate to good yields. Gratifyingly, indene could be easily converted into synthetically useful 3-indole-substituted indanone and indanol. Nonetheless, the successful isolation of a reaction intermediate highlights the crucial role of methanol in this reaction.
{"title":"Base-Assisted and Silica Gel-Promoted Indole-Substituted Indene Synthesis","authors":"Anurag Verma, Ruchir Kant, Nayan Ghosh","doi":"10.1021/acs.joc.5c00316","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00316","url":null,"abstract":"Herein, we report for the first time a transition-metal-free and mild protocol that requires inexpensive K<sub>2</sub>CO<sub>3</sub> and silica gel for direct access to polysubstituted indenes from readily obtainable starting precursors. Notably, sequential Michael addition, intramolecular cyclization, and silica gel-promoted nucleophilic substitution reactions afford the desired products. A broad range of indoles and other aromatic nucleophiles are well-tolerated, affording indenes in moderate to good yields. Gratifyingly, indene could be easily converted into synthetically useful 3-indole-substituted indanone and indanol. Nonetheless, the successful isolation of a reaction intermediate highlights the crucial role of methanol in this reaction.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"226 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758477","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}
引用次数: 0
Synthesis and Elaboration of Medium-Sized Ring Building Blocks Prepared via Cascade Ring Expansion Reactions 通过级联扩环反应制备的中型环状结构单元的合成与阐释
IF 4.354 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-04-01 DOI: 10.1021/acs.joc.5c00202
Haimei Zhou, Peter O’Brien, William P. Unsworth
A general approach is described for the synthesis and elaboration of medium-sized ring mono- and difunctionalized 8- or 9-membered ring lactone building blocks. The lactones are prepared via cascade ring expansion reactions and elaborated via Suzuki–Miyaura cross coupling and various N-functionalization reactions. This enables efficient access to diverse, medium-sized ring building blocks in a synthetically challenging and under-represented area of the pharmaceutical chemical space.
{"title":"Synthesis and Elaboration of Medium-Sized Ring Building Blocks Prepared via Cascade Ring Expansion Reactions","authors":"Haimei Zhou, Peter O’Brien, William P. Unsworth","doi":"10.1021/acs.joc.5c00202","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00202","url":null,"abstract":"A general approach is described for the synthesis and elaboration of medium-sized ring mono- and difunctionalized 8- or 9-membered ring lactone building blocks. The lactones are prepared via cascade ring expansion reactions and elaborated via Suzuki–Miyaura cross coupling and various <i>N</i>-functionalization reactions. This enables efficient access to diverse, medium-sized ring building blocks in a synthetically challenging and under-represented area of the pharmaceutical chemical space.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"38 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758478","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}
引用次数: 0
Mechanistic Insights into the Propagation Cycle of the Hofmann–Löffler–Freytag Reaction: Halogen vs Hydrogen Atom Transfer
IF 4.354 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-04-01 DOI: 10.1021/acs.joc.4c02997
Gabrijel Zubčić, Luka Andrijanić, Iva Džeba, Jiangyang You, Tomislav Friganović, Tomislav Portada, Kristina Pavić, Erim Bešić, Valerije Vrček, Davor Šakić
The Hofmann–Löffler–Freytag (HLF) reaction is a method that employs N-chlorinated precursors in radical-mediated rearrangement cycles to synthesize pyrrolidine rings and C–H functionalized products. This study aims to elucidate the mechanism of the propagation cycle, identify the rate-limiting step, and uncover the factors influencing the regioselectivity of the HLF reaction. Combining experimental techniques─laser flash photolysis (LFP), electron paramagnetic resonance (EPR), and nuclear magnetic resonance (NMR)─with computational density functional theory (DFT) calculations and kinetic modeling, we challenge the previous assumption that the hydrogen atom transfer (HAT) step was rate-limiting and regioselectivity was under both thermodynamic and kinetic control. We have identified that the halogen atom transfer (XAT) step in the propagation cycle of the HLF reaction follows pseudo-first-order kinetics and has the largest transition-state barrier. Additionally, we observed that regioselectivity is exclusively controlled by the intramolecular hydrogen atom transfer kinetics, while no thermodynamic preference exists in the formation of C6- and C5-chlorinated products. Our work predicts how to accelerate the HLF reaction and how we can control the regioselectivity by the smarter selection of substrates based on calculations, which could provide better control of the reaction when implemented in organic synthesis.
{"title":"Mechanistic Insights into the Propagation Cycle of the Hofmann–Löffler–Freytag Reaction: Halogen vs Hydrogen Atom Transfer","authors":"Gabrijel Zubčić, Luka Andrijanić, Iva Džeba, Jiangyang You, Tomislav Friganović, Tomislav Portada, Kristina Pavić, Erim Bešić, Valerije Vrček, Davor Šakić","doi":"10.1021/acs.joc.4c02997","DOIUrl":"https://doi.org/10.1021/acs.joc.4c02997","url":null,"abstract":"The Hofmann–Löffler–Freytag (HLF) reaction is a method that employs N-chlorinated precursors in radical-mediated rearrangement cycles to synthesize pyrrolidine rings and C–H functionalized products. This study aims to elucidate the mechanism of the propagation cycle, identify the rate-limiting step, and uncover the factors influencing the regioselectivity of the HLF reaction. Combining experimental techniques─laser flash photolysis (LFP), electron paramagnetic resonance (EPR), and nuclear magnetic resonance (NMR)─with computational density functional theory (DFT) calculations and kinetic modeling, we challenge the previous assumption that the hydrogen atom transfer (HAT) step was rate-limiting and regioselectivity was under both thermodynamic and kinetic control. We have identified that the halogen atom transfer (XAT) step in the propagation cycle of the HLF reaction follows pseudo-first-order kinetics and has the largest transition-state barrier. Additionally, we observed that regioselectivity is exclusively controlled by the intramolecular hydrogen atom transfer kinetics, while no thermodynamic preference exists in the formation of C<sub>6</sub>- and C<sub>5</sub>-chlorinated products. Our work predicts how to accelerate the HLF reaction and how we can control the regioselectivity by the smarter selection of substrates based on calculations, which could provide better control of the reaction when implemented in organic synthesis.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"58 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745240","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}
引用次数: 0
Synthesizing Chiral Vicinal Bisphosphine Derivatives through Hydrophosphinylation and Asymmetric Protonation of Secondary Phosphine Sulfides with Vinylphosphine Oxides 通过仲膦硫化物与乙烯基氧化膦的氢化膦酰化和不对称质子化合成手性手性双膦衍生物
IF 4.354 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-04-01 DOI: 10.1021/acs.joc.5c00414
Eiki Hirota, Shin-ichi Hirashima, Chika Tadasue, Anna Suzuki, Yasuyuki Matsushima, Kosuke Nakashima, Tsuyoshi Miura
Herein, we report bifunctional iminophosphorane-catalyzed hydrophosphinylation and asymmetric protonation of secondary phosphine sulfides with vinylphosphine oxides. This reaction efficiently afforded chiral vicinal bisphosphine derivatives in high yields with excellent enantioselectivities (up to 99% yield and 95% ee). Furthermore, the produced chiral vicinal bisphosphine derivatives could be readily transformed into vicinal bisphosphines and vicinal bisphosphine monosulfides. This study presents the first methodology for using secondary phosphine sulfides as pronucleophiles in asymmetric protonation reactions.
{"title":"Synthesizing Chiral Vicinal Bisphosphine Derivatives through Hydrophosphinylation and Asymmetric Protonation of Secondary Phosphine Sulfides with Vinylphosphine Oxides","authors":"Eiki Hirota, Shin-ichi Hirashima, Chika Tadasue, Anna Suzuki, Yasuyuki Matsushima, Kosuke Nakashima, Tsuyoshi Miura","doi":"10.1021/acs.joc.5c00414","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00414","url":null,"abstract":"Herein, we report bifunctional iminophosphorane-catalyzed hydrophosphinylation and asymmetric protonation of secondary phosphine sulfides with vinylphosphine oxides. This reaction efficiently afforded chiral vicinal bisphosphine derivatives in high yields with excellent enantioselectivities (up to 99% yield and 95% ee). Furthermore, the produced chiral vicinal bisphosphine derivatives could be readily transformed into vicinal bisphosphines and vicinal bisphosphine monosulfides. This study presents the first methodology for using secondary phosphine sulfides as pronucleophiles in asymmetric protonation reactions.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"38 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758487","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}
引用次数: 0
Au(I) /Brønsted Acid Relay-Catalyzed Benzannulation Reaction of Alkynylbenzaldehydes and Styrenes for the Synthesis of Substituted Naphthalenes
IF 4.354 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-04-01 DOI: 10.1021/acs.joc.4c03186
Yuanzhen Xu, Shaolong Zheng, Yun Li
We report herein an Au(I) /Brønsted acid relay-catalyzed tandem benzannulation reaction of alkynylbenzaldehydes and styrenes for the synthesis of substituted naphthalenes. This reaction sequence involves Au(I)-catalyzed alkyne cycloisomerization, oxa-[4 + 2]-cycloaddition, α-ketol rearrangement, and aromatization to access substituted naphthalenes in moderate-to-good yields. The resulting substituted naphthalenes are further subjected to Brønsted acid catalysis, promoting Friedel–Crafts reactions to form chrysene derivatives in excellent yields.
{"title":"Au(I) /Brønsted Acid Relay-Catalyzed Benzannulation Reaction of Alkynylbenzaldehydes and Styrenes for the Synthesis of Substituted Naphthalenes","authors":"Yuanzhen Xu, Shaolong Zheng, Yun Li","doi":"10.1021/acs.joc.4c03186","DOIUrl":"https://doi.org/10.1021/acs.joc.4c03186","url":null,"abstract":"We report herein an Au(I) /Brønsted acid relay-catalyzed tandem benzannulation reaction of alkynylbenzaldehydes and styrenes for the synthesis of substituted naphthalenes. This reaction sequence involves Au(I)-catalyzed alkyne cycloisomerization, oxa-[4 + 2]-cycloaddition, α-ketol rearrangement, and aromatization to access substituted naphthalenes in moderate-to-good yields. The resulting substituted naphthalenes are further subjected to Brønsted acid catalysis, promoting Friedel–Crafts reactions to form chrysene derivatives in excellent yields.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"15 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745264","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}
引用次数: 0
From Cortisone to Enlicitide: A Journey of Synthetic Chemistry Innovations at Merck
IF 4.354 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-04-01 DOI: 10.1021/acs.joc.4c02919
Louis-Charles Campeau
Necessity is the mother of invention. Most synthetic chemistry innovations are driven by our desire to make molecules. In the first half of the 20th century, much of this work was inspired by natural products, but as we started to understand the impact that specific molecules could have on biology and human health, a new stimulus for invention appeared. The pharmaceutical industry first brought mass production and formulation of natural products for medicinal purposes but quickly started tinkering with molecular structure to modify compounds’ properties, eventually designing molecules from scratch. This necessity for invention of new molecules to improve human health and to manufacture them on large scale is an excellent stimulus for synthetic chemistry innovations. In this Perspective, examples from Merck’s chemistry groups are used to highlight the types of innovations that can arise from these endeavors.
{"title":"From Cortisone to Enlicitide: A Journey of Synthetic Chemistry Innovations at Merck","authors":"Louis-Charles Campeau","doi":"10.1021/acs.joc.4c02919","DOIUrl":"https://doi.org/10.1021/acs.joc.4c02919","url":null,"abstract":"Necessity is the mother of invention. Most synthetic chemistry innovations are driven by our desire to make molecules. In the first half of the 20th century, much of this work was inspired by natural products, but as we started to understand the impact that specific molecules could have on biology and human health, a new stimulus for invention appeared. The pharmaceutical industry first brought mass production and formulation of natural products for medicinal purposes but quickly started tinkering with molecular structure to modify compounds’ properties, eventually designing molecules from scratch. This necessity for invention of new molecules to improve human health and to manufacture them on large scale is an excellent stimulus for synthetic chemistry innovations. In this Perspective, examples from Merck’s chemistry groups are used to highlight the types of innovations that can arise from these endeavors.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"73 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758476","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}
引用次数: 0
期刊
Journal of Organic Chemistry
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