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Total Synthesis of (-)-Elodeoidins A and B.
IF 8.5
JACS Au Pub Date : 2025-03-12 eCollection Date: 2025-03-24 DOI: 10.1021/jacsau.5c00201
Chungwoo Lee, Gyumin Kang, Jaehyun You, Taewan Kim, Hee-Seung Lee, Yoonsu Park, Sunkyu Han
{"title":"Total Synthesis of (-)-Elodeoidins A and B.","authors":"Chungwoo Lee, Gyumin Kang, Jaehyun You, Taewan Kim, Hee-Seung Lee, Yoonsu Park, Sunkyu Han","doi":"10.1021/jacsau.5c00201","DOIUrl":"10.1021/jacsau.5c00201","url":null,"abstract":"<p><p>Biomimicry has long been a valuable approach for designing efficient synthetic strategies in complex natural product synthesis. However, abiotic yet powerful transforms can significantly streamline the synthesis by introducing greater convergence to the synthetic route. Herein, we delineate a convergent total synthesis of elodeoidins A and B, enabled by a cross-dehydrogenative coupling (CDC) reaction between an aldehyde and an electron-deficient olefin. The CDC reaction operating under the newly discovered reaction conditions proceeds via distinct concerted deprotonation within the formal Cu(III) catalytic complex. Furthermore, the total synthesis of both structural candidates of elodeoidin B revealed that the natural product exists as a mixture of epimers at the C8 stereocenter.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 3","pages":"1096-1103"},"PeriodicalIF":8.5,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11938003/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143733656","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Intermediate-Temperature Reverse Water-Gas Shift under Process-Relevant Conditions Catalyzed by Dispersed Alkali Carbonates.
IF 8.5
JACS Au Pub Date : 2025-03-12 eCollection Date: 2025-03-24 DOI: 10.1021/jacsau.5c00127
Kesha N Tamakuwala, Robert P Kennedy, Chastity S Li, Benjamin Mutz, Peter Boller, Simon R Bare, Matthew W Kanan
{"title":"Intermediate-Temperature Reverse Water-Gas Shift under Process-Relevant Conditions Catalyzed by Dispersed Alkali Carbonates.","authors":"Kesha N Tamakuwala, Robert P Kennedy, Chastity S Li, Benjamin Mutz, Peter Boller, Simon R Bare, Matthew W Kanan","doi":"10.1021/jacsau.5c00127","DOIUrl":"10.1021/jacsau.5c00127","url":null,"abstract":"<p><p>Current reverse water-gas shift (RWGS) technologies require extreme temperatures of >900 °C. The ability to perform RWGS at lower temperatures could open new opportunities for sustainable chemical and fuel production, but most catalyst materials produce methane and coke at lower temperatures, especially at elevated pressures targeted for industrial processes. Here we show that transition-metal-free catalysts composed of K<sub>2</sub>CO<sub>3</sub> or Na<sub>2</sub>CO<sub>3</sub> dispersed on commercial γ-Al<sub>2</sub>O<sub>3</sub> supports (K<sub>2</sub>CO<sub>3</sub>/γ-Al<sub>2</sub>O<sub>3</sub> and Na<sub>2</sub>CO<sub>3</sub>/γ-Al<sub>2</sub>O<sub>3</sub>) are highly effective RWGS catalysts in the intermediate-temperature regime. At a high gas hourly space velocity of 30,000 h<sup>-1</sup> and operating pressure of 10 bar, K<sub>2</sub>CO<sub>3</sub>/γ-Al<sub>2</sub>O<sub>3</sub> reached RWGS equilibrium-limited CO<sub>2</sub> conversion at 550 °C and was 100% selective for CO at all temperatures tested (up to 700 °C). Na<sub>2</sub>CO<sub>3</sub>/γ-Al<sub>2</sub>O<sub>3</sub> was also 100% CO-selective and only slightly less active. Both catalysts were stable for hundreds of hours on stream at 525 °C and tolerated large quantities of methane and propane impurity in the CO<sub>2</sub>/H<sub>2</sub> feed. The unique performance attributes, combined with the low-cost components and extremely simple synthesis, make dispersed carbonate RWGS catalysts attractive options for industrial application.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 3","pages":"1083-1089"},"PeriodicalIF":8.5,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11937989/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143733706","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Total Synthesis of (−)-Elodeoidins A and B
IF 8.5
JACS Au Pub Date : 2025-03-12 DOI: 10.1021/jacsau.5c0020110.1021/jacsau.5c00201
Chungwoo Lee, Gyumin Kang, Jaehyun You, Taewan Kim, Hee-Seung Lee, Yoonsu Park* and Sunkyu Han*, 
{"title":"Total Synthesis of (−)-Elodeoidins A and B","authors":"Chungwoo Lee,&nbsp;Gyumin Kang,&nbsp;Jaehyun You,&nbsp;Taewan Kim,&nbsp;Hee-Seung Lee,&nbsp;Yoonsu Park* and Sunkyu Han*,&nbsp;","doi":"10.1021/jacsau.5c0020110.1021/jacsau.5c00201","DOIUrl":"https://doi.org/10.1021/jacsau.5c00201https://doi.org/10.1021/jacsau.5c00201","url":null,"abstract":"<p >Biomimicry has long been a valuable approach for designing efficient synthetic strategies in complex natural product synthesis. However, abiotic yet powerful transforms can significantly streamline the synthesis by introducing greater convergence to the synthetic route. Herein, we delineate a convergent total synthesis of elodeoidins A and B, enabled by a cross-dehydrogenative coupling (CDC) reaction between an aldehyde and an electron-deficient olefin. The CDC reaction operating under the newly discovered reaction conditions proceeds via distinct concerted deprotonation within the formal Cu(III) catalytic complex. Furthermore, the total synthesis of both structural candidates of elodeoidin B revealed that the natural product exists as a mixture of epimers at the C8 stereocenter.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 3","pages":"1096–1103 1096–1103"},"PeriodicalIF":8.5,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.5c00201","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675920","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Intermediate-Temperature Reverse Water–Gas Shift under Process-Relevant Conditions Catalyzed by Dispersed Alkali Carbonates
IF 8.5
JACS Au Pub Date : 2025-03-12 DOI: 10.1021/jacsau.5c0012710.1021/jacsau.5c00127
Kesha N. Tamakuwala, Robert P. Kennedy, Chastity S. Li, Benjamin Mutz, Peter Boller, Simon R. Bare and Matthew W. Kanan*, 
{"title":"Intermediate-Temperature Reverse Water–Gas Shift under Process-Relevant Conditions Catalyzed by Dispersed Alkali Carbonates","authors":"Kesha N. Tamakuwala,&nbsp;Robert P. Kennedy,&nbsp;Chastity S. Li,&nbsp;Benjamin Mutz,&nbsp;Peter Boller,&nbsp;Simon R. Bare and Matthew W. Kanan*,&nbsp;","doi":"10.1021/jacsau.5c0012710.1021/jacsau.5c00127","DOIUrl":"https://doi.org/10.1021/jacsau.5c00127https://doi.org/10.1021/jacsau.5c00127","url":null,"abstract":"<p >Current reverse water–gas shift (RWGS) technologies require extreme temperatures of &gt;900 °C. The ability to perform RWGS at lower temperatures could open new opportunities for sustainable chemical and fuel production, but most catalyst materials produce methane and coke at lower temperatures, especially at elevated pressures targeted for industrial processes. Here we show that transition-metal-free catalysts composed of K<sub>2</sub>CO<sub>3</sub> or Na<sub>2</sub>CO<sub>3</sub> dispersed on commercial γ-Al<sub>2</sub>O<sub>3</sub> supports (K<sub>2</sub>CO<sub>3</sub>/γ-Al<sub>2</sub>O<sub>3</sub> and Na<sub>2</sub>CO<sub>3</sub>/γ-Al<sub>2</sub>O<sub>3</sub>) are highly effective RWGS catalysts in the intermediate-temperature regime. At a high gas hourly space velocity of 30,000 h<sup>–1</sup> and operating pressure of 10 bar, K<sub>2</sub>CO<sub>3</sub>/γ-Al<sub>2</sub>O<sub>3</sub> reached RWGS equilibrium-limited CO<sub>2</sub> conversion at 550 °C and was 100% selective for CO at all temperatures tested (up to 700 °C). Na<sub>2</sub>CO<sub>3</sub>/γ-Al<sub>2</sub>O<sub>3</sub> was also 100% CO-selective and only slightly less active. Both catalysts were stable for hundreds of hours on stream at 525 °C and tolerated large quantities of methane and propane impurity in the CO<sub>2</sub>/H<sub>2</sub> feed. The unique performance attributes, combined with the low-cost components and extremely simple synthesis, make dispersed carbonate RWGS catalysts attractive options for industrial application.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 3","pages":"1083–1089 1083–1089"},"PeriodicalIF":8.5,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.5c00127","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675796","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Data-Driven Search Algorithm for Discovery of Synthesizable Zeolitic Imidazolate Frameworks
IF 8.5
JACS Au Pub Date : 2025-03-07 DOI: 10.1021/jacsau.5c0007710.1021/jacsau.5c00077
Soochan Lee, Hyein Jeong, Sungyeop Jung, Yeongjin Kim, Eunchan Cho, Joohan Nam, D. ChangMo Yang, Dong Yun Shin, Jung-Hoon Lee, Hyunchul Oh and Wonyoung Choe*, 
{"title":"Data-Driven Search Algorithm for Discovery of Synthesizable Zeolitic Imidazolate Frameworks","authors":"Soochan Lee,&nbsp;Hyein Jeong,&nbsp;Sungyeop Jung,&nbsp;Yeongjin Kim,&nbsp;Eunchan Cho,&nbsp;Joohan Nam,&nbsp;D. ChangMo Yang,&nbsp;Dong Yun Shin,&nbsp;Jung-Hoon Lee,&nbsp;Hyunchul Oh and Wonyoung Choe*,&nbsp;","doi":"10.1021/jacsau.5c0007710.1021/jacsau.5c00077","DOIUrl":"https://doi.org/10.1021/jacsau.5c00077https://doi.org/10.1021/jacsau.5c00077","url":null,"abstract":"<p >Zeolitic imidazolate frameworks (ZIFs), metal–organic analogues of zeolites, hold great potential for carbon-neutral applications due to their exceptional stability and porosity. However, ZIF discovery has been hindered by the limited topologies resulting from a mismatch between numerous predicted and few synthesized zeolitic networks. To address this, we propose a data-driven search algorithm using structural descriptors of known materials as a screening tool. From over 4 million zeolite structures, we identified potential ZIF candidates based on O–T–O angle differences, vertex symbols, and T–O–T angles. Energy calculations facilitated the ranking of ZIFs by their synthesizability, leading to the successful synthesis of three ZIFs with two novel topologies: UZIF-31 (<i>uft</i>1) and UZIF-32, -33 (<i>uft</i>2). Notably, UZIF-33 exhibited remarkable CO<sub>2</sub> selective adsorption. This study highlights the synergistic potential of combining structural predictions with chemical intuition to advance material discovery.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 3","pages":"1460–1470 1460–1470"},"PeriodicalIF":8.5,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.5c00077","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675827","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Catalyst-Transfer Macrocyclization Protocol: Synthesis of π-Conjugated Azaparacyclophanes Made Easy
IF 8.5
JACS Au Pub Date : 2025-03-07 DOI: 10.1021/jacsau.5c0010910.1021/jacsau.5c00109
Josue Ayuso-Carrillo,  and , Davide Bonifazi*, 
{"title":"Catalyst-Transfer Macrocyclization Protocol: Synthesis of π-Conjugated Azaparacyclophanes Made Easy","authors":"Josue Ayuso-Carrillo,&nbsp; and ,&nbsp;Davide Bonifazi*,&nbsp;","doi":"10.1021/jacsau.5c0010910.1021/jacsau.5c00109","DOIUrl":"https://doi.org/10.1021/jacsau.5c00109https://doi.org/10.1021/jacsau.5c00109","url":null,"abstract":"<p >The present Protocol describes the application of the catalyst-transfer macrocyclization (CTM) reaction, focusing on the synthesis of aza[1<sub>n</sub>]paracyclophanes (APCs). APCs are fully π-conjugated shape-persistent macrocycles with potential supramolecular chemistry and materials science applications. This method leverages the Pd-catalyzed Buchwald–Hartwig cross-coupling reaction to selectively form π-conjugated cyclic structures, a significant advancement due to its efficiency, versatility, and scalability. Overall, this Article highlights the following attributes of the CTM method: a) Efficiency and Yield: The CTM method works at mild temperatures (40 °C) and short reaction times (≥2 h), producing high yields of APCs (&gt;75% macrocycles). It avoids the typical high-dilution conditions, making it more practical for large-scale applications. b) Versatility: The method allows the synthesis of APCs with diverse endocyclic and exocyclic functionalities and ring sizes (typically from 4- to 9-membered rings), expanding the chemical space for these compounds. This flexibility is crucial for tailoring APC properties for specific applications. c) Scalability and Reproducibility: Unlike many macrocyclization reactions, which require highly dilute conditions, CTM can perform under concentrated regimes (35–350 mM), making it more suitable for large-scale applications. d) Applications in Materials Science: APCs are noted for their potential in optoelectronic applications due to their π-conjugated structures, which are helpful in organic semiconductors, light-harvesting systems, and other advanced materials. This approach addresses the challenge of complicated multistep syntheses that have hindered the widespread integration of APCs into functional devices. A step-by-step guide to preparing exemplary APCs, including troubleshooting, is provided with photographic illustrations.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 3","pages":"1482–1498 1482–1498"},"PeriodicalIF":8.5,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.5c00109","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675846","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Computational Modeling of the Mobility, Stability, and Al Positioning Ability of Cyclic Cationic Organic Structure-Directing Agents in AEI Zeolite
IF 8.5
JACS Au Pub Date : 2025-03-07 DOI: 10.1021/jacsau.5c0009410.1021/jacsau.5c00094
Pau Ferri, Pieter Cnudde, Manuel Moliner, Veronique van Speybroeck* and Mercedes Boronat*, 
{"title":"Computational Modeling of the Mobility, Stability, and Al Positioning Ability of Cyclic Cationic Organic Structure-Directing Agents in AEI Zeolite","authors":"Pau Ferri,&nbsp;Pieter Cnudde,&nbsp;Manuel Moliner,&nbsp;Veronique van Speybroeck* and Mercedes Boronat*,&nbsp;","doi":"10.1021/jacsau.5c0009410.1021/jacsau.5c00094","DOIUrl":"https://doi.org/10.1021/jacsau.5c00094https://doi.org/10.1021/jacsau.5c00094","url":null,"abstract":"<p >The stability and mobility of a set of organic structure-directing agents (OSDAs) with different molecular geometries and charge distribution confined within the pear-like cavities of neutral and Al-containing models of AEI zeolites have been investigated by using static density functional theory calculations and ab initio molecular dynamics simulations. The objective is to identify the role of electrostatic interactions between the OSDAs’ positive charge at N<sup>+</sup> atoms and the anionic framework AlO<sub>4</sub><sup>–</sup> centers on the preferential stabilization of Al at specific crystallographic positions, opening the possibility to modulate the Al distribution in AEI zeolites. We find that several classical piperidinium-based OSDAs with diverse methyl-substituent patterns in the N-containing ring but a symmetrical charge distribution, as well as bulkier nonclassical azoniabicycle-heptane-based OSDAs with the positive charge asymmetrically located at one side of the molecule, behave similarly. All of them remain almost immobile at the center of the <i>aei</i> cavity along the simulations and always stabilize Al preferentially at the T1 crystallographic position. In contrast, an azabicyclo-octane-based OSDA with the positive charge located outside a cyclo-octane ring lacking substituents exhibits an enhanced mobility that includes full rotation within the <i>aei</i> cage and the ability to reach the regions of the cavity not accessible to the other OSDAs investigated. As a result, this highly mobile OSDA preferentially stabilizes Al in the T3 site, which might lead to differences in catalyst activity and stability for zeolite samples synthesized using this OSDA.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 3","pages":"1471–1481 1471–1481"},"PeriodicalIF":8.5,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.5c00094","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675829","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Data-Driven Search Algorithm for Discovery of Synthesizable Zeolitic Imidazolate Frameworks.
IF 8.5
JACS Au Pub Date : 2025-03-07 eCollection Date: 2025-03-24 DOI: 10.1021/jacsau.5c00077
Soochan Lee, Hyein Jeong, Sungyeop Jung, Yeongjin Kim, Eunchan Cho, Joohan Nam, D ChangMo Yang, Dong Yun Shin, Jung-Hoon Lee, Hyunchul Oh, Wonyoung Choe
{"title":"Data-Driven Search Algorithm for Discovery of Synthesizable Zeolitic Imidazolate Frameworks.","authors":"Soochan Lee, Hyein Jeong, Sungyeop Jung, Yeongjin Kim, Eunchan Cho, Joohan Nam, D ChangMo Yang, Dong Yun Shin, Jung-Hoon Lee, Hyunchul Oh, Wonyoung Choe","doi":"10.1021/jacsau.5c00077","DOIUrl":"10.1021/jacsau.5c00077","url":null,"abstract":"<p><p>Zeolitic imidazolate frameworks (ZIFs), metal-organic analogues of zeolites, hold great potential for carbon-neutral applications due to their exceptional stability and porosity. However, ZIF discovery has been hindered by the limited topologies resulting from a mismatch between numerous predicted and few synthesized zeolitic networks. To address this, we propose a data-driven search algorithm using structural descriptors of known materials as a screening tool. From over 4 million zeolite structures, we identified potential ZIF candidates based on O-T-O angle differences, vertex symbols, and T-O-T angles. Energy calculations facilitated the ranking of ZIFs by their synthesizability, leading to the successful synthesis of three ZIFs with two novel topologies: UZIF-31 (<i>uft</i>1) and UZIF-32, -33 (<i>uft</i>2). Notably, UZIF-33 exhibited remarkable CO<sub>2</sub> selective adsorption. This study highlights the synergistic potential of combining structural predictions with chemical intuition to advance material discovery.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 3","pages":"1460-1470"},"PeriodicalIF":8.5,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11938011/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143733678","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Photoredox-Catalyzed Radical Cyclization of Unactivated Alkene-Substituted β-Ketoesters Enabled Asymmetric Total Synthesis of Tricyclic Prostaglandin D2 Metabolite Methyl Ester.
IF 8.5
JACS Au Pub Date : 2025-03-07 eCollection Date: 2025-03-24 DOI: 10.1021/jacsau.4c01268
Miao Xiao, Qiaoli Shang, Liuyang Pu, Zheyuan Wang, Lei Zhu, Zhen Yang, Jun Huang
{"title":"Photoredox-Catalyzed Radical Cyclization of Unactivated Alkene-Substituted β-Ketoesters Enabled Asymmetric Total Synthesis of Tricyclic Prostaglandin D<sub>2</sub> Metabolite Methyl Ester.","authors":"Miao Xiao, Qiaoli Shang, Liuyang Pu, Zheyuan Wang, Lei Zhu, Zhen Yang, Jun Huang","doi":"10.1021/jacsau.4c01268","DOIUrl":"10.1021/jacsau.4c01268","url":null,"abstract":"<p><p>Regio- and stereoselective photoredox-catalyzed cyclizations of alkene-substituted β-ketoesters have been accomplished for the synthesis of polyfunctionalized cyclopentanones. This was achieved using 2,3,5,6-tetrakis(carbazol-9-yl)-1,4-dicyanobenzene (4CzTPN) and 2,4,6-triisopropyl-thiophenol as cocatalysts under illumination of a blue-light-emitting-diode at ambient temperature. The developed chemistry was successfully applied in the enantioselective total synthesis of the tricyclic prostaglandin D<sub>2</sub> metabolite (tricyclic-PGDM) methyl ester, which was completed in 9 steps with an overall yield of 7%.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 3","pages":"1367-1375"},"PeriodicalIF":8.5,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11937966/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143733840","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Catalyst-Transfer Macrocyclization Protocol: Synthesis of π-Conjugated Azaparacyclophanes Made Easy.
IF 8.5
JACS Au Pub Date : 2025-03-07 eCollection Date: 2025-03-24 DOI: 10.1021/jacsau.5c00109
Josue Ayuso-Carrillo, Davide Bonifazi
{"title":"Catalyst-Transfer Macrocyclization Protocol: Synthesis of π-Conjugated Azaparacyclophanes Made Easy.","authors":"Josue Ayuso-Carrillo, Davide Bonifazi","doi":"10.1021/jacsau.5c00109","DOIUrl":"10.1021/jacsau.5c00109","url":null,"abstract":"<p><p>The present Protocol describes the application of the catalyst-transfer macrocyclization (CTM) reaction, focusing on the synthesis of aza[1<sub>n</sub>]paracyclophanes (APCs). APCs are fully π-conjugated shape-persistent macrocycles with potential supramolecular chemistry and materials science applications. This method leverages the Pd-catalyzed Buchwald-Hartwig cross-coupling reaction to selectively form π-conjugated cyclic structures, a significant advancement due to its efficiency, versatility, and scalability. Overall, this Article highlights the following attributes of the CTM method: a) Efficiency and Yield: The CTM method works at mild temperatures (40 °C) and short reaction times (≥2 h), producing high yields of APCs (>75% macrocycles). It avoids the typical high-dilution conditions, making it more practical for large-scale applications. b) Versatility: The method allows the synthesis of APCs with diverse endocyclic and exocyclic functionalities and ring sizes (typically from 4- to 9-membered rings), expanding the chemical space for these compounds. This flexibility is crucial for tailoring APC properties for specific applications. c) Scalability and Reproducibility: Unlike many macrocyclization reactions, which require highly dilute conditions, CTM can perform under concentrated regimes (35-350 mM), making it more suitable for large-scale applications. d) Applications in Materials Science: APCs are noted for their potential in optoelectronic applications due to their π-conjugated structures, which are helpful in organic semiconductors, light-harvesting systems, and other advanced materials. This approach addresses the challenge of complicated multistep syntheses that have hindered the widespread integration of APCs into functional devices. A step-by-step guide to preparing exemplary APCs, including troubleshooting, is provided with photographic illustrations.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 3","pages":"1482-1498"},"PeriodicalIF":8.5,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11937971/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143733645","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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