To clarify the relationship between the host‐guest complexation and enantioselectivity of an asymmetric reaction, we studied the impacts of pillar[5]arene‐based host–guest chemistry on the asymmetric catalytic synthesis of cyclic dihydroquinazolinones from aldehydes, where the aldehydes meanwhile acted as guests. The addition of different pillar[5]arenes cannot only adjust the reactivity of the substrates but also change the enantiomeric excess of the products. The magnitude of such impacts is influenced by several factors, including the solvent, the temperature, the catalyst, the usage and kind of pillararenes, and the structure of aldehydes. When the pillararene‐substrate interactions are strong in the reaction systems, the ee variations of products are mainly decided by the guests, aldehydes, whereas the reaction activities are mainly affected by the hosts, pillar[5]arenes.
{"title":"Influence of Pillararene‐Based Host–Guest Chemistry on the Enantioselective Synthesis of 2,3‐Dihydroquinazolinones","authors":"Dan Zhou, Menglan Ma, Jiyong Liu, Yuhang Sheng, Peiling Zhang, Shuping Wang, Feihe Huang, Shijun Li, Zibin Zhang","doi":"10.1002/ejoc.202500081","DOIUrl":"https://doi.org/10.1002/ejoc.202500081","url":null,"abstract":"To clarify the relationship between the host‐guest complexation and enantioselectivity of an asymmetric reaction, we studied the impacts of pillar[5]arene‐based host–guest chemistry on the asymmetric catalytic synthesis of cyclic dihydroquinazolinones from aldehydes, where the aldehydes meanwhile acted as guests. The addition of different pillar[5]arenes cannot only adjust the reactivity of the substrates but also change the enantiomeric excess of the products. The magnitude of such impacts is influenced by several factors, including the solvent, the temperature, the catalyst, the usage and kind of pillararenes, and the structure of aldehydes. When the pillararene‐substrate interactions are strong in the reaction systems, the ee variations of products are mainly decided by the guests, aldehydes, whereas the reaction activities are mainly affected by the hosts, pillar[5]arenes.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"13 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143443724","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A novel series of 4H-imidazol-4-ones, designated as compounds 5(a–l), were synthesized from phenylalanine and tyrosine. This synthesis involved derivatization of amino acids with phenylacetyl chloride, followed by cyclocondensation with aromatic amines using PCl3 and a deep eutectic solvent as both catalyst and solvent. Amide intermediates were first produced via the Schotten-Baumann reaction. These intermediates then underwent cyclization in the presence of PCl3 and deep-eutectic solvent, leading to the formation of imidazolones as potent antioxidants. The newly synthesized compounds were evaluated for their antioxidant activities using several electron transfer-based assays, including DPPH, ABTS, FRAP, and CUPRAC. Among the tested compounds, compound 5i exhibited excellent antioxidant activity compared to the standard reference drugs, ascorbic acid and Trolox.
{"title":"Synthesis of 4H-imidazol-4-ones from α-Amino acids, and their Antioxidant Activities using Electron Transfer Methods","authors":"Mukherjee Singh Okram, Mayanglambam Maneeta Devi, Keisham Subharani Devi, Thangjam Linda Devi, Thokchom Prasanta Singh","doi":"10.1002/ejoc.202401449","DOIUrl":"https://doi.org/10.1002/ejoc.202401449","url":null,"abstract":"A novel series of 4H-imidazol-4-ones, designated as compounds 5(a–l), were synthesized from phenylalanine and tyrosine. This synthesis involved derivatization of amino acids with phenylacetyl chloride, followed by cyclocondensation with aromatic amines using PCl3 and a deep eutectic solvent as both catalyst and solvent. Amide intermediates were first produced via the Schotten-Baumann reaction. These intermediates then underwent cyclization in the presence of PCl3 and deep-eutectic solvent, leading to the formation of imidazolones as potent antioxidants. The newly synthesized compounds were evaluated for their antioxidant activities using several electron transfer-based assays, including DPPH, ABTS, FRAP, and CUPRAC. Among the tested compounds, compound 5i exhibited excellent antioxidant activity compared to the standard reference drugs, ascorbic acid and Trolox.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"66 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435699","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hilal Ahmad Khan, S Naveen Kumar, Ananth Kumar R, Gruhapriya Jelakam, Chinnappan Sivasankar
Imidazole and substituted imidazoles have drawn much attention owing to their superior biological functions. In this regard, devising a synthetic strategy to improve viability, easy to handle and more yield is challenging task for synthetic chemists. Herein we report a new synthetic strategy for the synthesis of imidazol‐4‐ones from hydrazides and α‐diazoesters using Cu(I) metal catalyst. In the absence of the Cu(I) catalyst or even utilizing any other metal catalyst, the imine bond formation between the terminal N of hydrazides and carbene was observed. Therefore, Cu(I) salt catalysis this reaction in a unique way. The reaction proceeds via the cleavage of the C‐N bond of the hydrazide followed by cyclization and yielded the expected product. We have also explored the substrate scope of our strategy and obtained excellent yields. We have isolated the products in a pure form and fully characterized using sophisticated analytical and spectroscopic techniques including single crystal X‐Ray analysis.
{"title":"A new approach towards the synthesis of imidazol‐4‐ones using α‐diazoesters and hydrazide catalysed by Cu(I) salt","authors":"Hilal Ahmad Khan, S Naveen Kumar, Ananth Kumar R, Gruhapriya Jelakam, Chinnappan Sivasankar","doi":"10.1002/ejoc.202401395","DOIUrl":"https://doi.org/10.1002/ejoc.202401395","url":null,"abstract":"Imidazole and substituted imidazoles have drawn much attention owing to their superior biological functions. In this regard, devising a synthetic strategy to improve viability, easy to handle and more yield is challenging task for synthetic chemists. Herein we report a new synthetic strategy for the synthesis of imidazol‐4‐ones from hydrazides and α‐diazoesters using Cu(I) metal catalyst. In the absence of the Cu(I) catalyst or even utilizing any other metal catalyst, the imine bond formation between the terminal N of hydrazides and carbene was observed. Therefore, Cu(I) salt catalysis this reaction in a unique way. The reaction proceeds via the cleavage of the C‐N bond of the hydrazide followed by cyclization and yielded the expected product. We have also explored the substrate scope of our strategy and obtained excellent yields. We have isolated the products in a pure form and fully characterized using sophisticated analytical and spectroscopic techniques including single crystal X‐Ray analysis.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"29 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435380","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ivan Nuzhdin, Arina Murashkina, Stanislav Bezzubov, Alexander Mitrofanov, Irina Beletskaya
In this study, we have developed an approach for the selective two‐step synthesis of phosphoryl‐substituted 4‐quinolones and phosphoryl‐substituted 3‐indolinones. This was achieved through the reaction of (3‐(2‐iodoaryl)‐3‐oxoprop‐1‐yn‐1‐yl)phosphonates with anilines followed by Cu‐catalyzed intramolecular cyclization of the intermediately formed regioisomeric enamines, which are selectively formed under neat conditions or in the presence of a gold complex as a catalyst. This method allows for the synthesis of a series of phosphoryl‐substituted 4‐quinolones and phosphoryl‐substituted 3‐indolinones in good yields.
{"title":"Divergent One‐Pot Two‐Step Synthesis of Phosphoryl‐Substituted 4‐Quinolones and 3‐Indolinones","authors":"Ivan Nuzhdin, Arina Murashkina, Stanislav Bezzubov, Alexander Mitrofanov, Irina Beletskaya","doi":"10.1002/ejoc.202401423","DOIUrl":"https://doi.org/10.1002/ejoc.202401423","url":null,"abstract":"In this study, we have developed an approach for the selective two‐step synthesis of phosphoryl‐substituted 4‐quinolones and phosphoryl‐substituted 3‐indolinones. This was achieved through the reaction of (3‐(2‐iodoaryl)‐3‐oxoprop‐1‐yn‐1‐yl)phosphonates with anilines followed by Cu‐catalyzed intramolecular cyclization of the intermediately formed regioisomeric enamines, which are selectively formed under neat conditions or in the presence of a gold complex as a catalyst. This method allows for the synthesis of a series of phosphoryl‐substituted 4‐quinolones and phosphoryl‐substituted 3‐indolinones in good yields.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"49 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435403","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Maria Luisa Gelmi, Francesco Anastasi, Raffaella Bucci, Alessandro Contini, Donatella Nava, Gabriele Fontana, Fabio Usubelli, Meng Zhou
A refresh and improvement of the well‐known myo‐inositol chemistry is reported here, setting up a new synthetic protocol to obtain orthogonally protected compounds, with a special focus on the preparation of 2‐O‐alkylated compounds. A gram scale synthesis of the 2‐allyl compound was performed and optimized in terms of yield. This intermediate is the precursor of chiro‐1‐inosose, for which synthetic procedures are lacking. Taking advantage of the easily handled allyl group, we were able to transform this keto compound into both the 1,2‐diketone and 3‐deoxy‐1,2‐diketone, intermediates of biological transformations used in several patented applications. Finally, to access poly‐hydroxylated‐(aminomethyl)cyclohexane compounds, the reaction of the keto compound with cyanide was optimized, affording cyanohydrins obtained as single stereoisomer, the precursor of the above compound.
{"title":"Improved Chemistry of myo‐Inositol: a New Synthetic Strategy to Protected 1‐Keto‐ and 1,2‐Keto‐derivatives","authors":"Maria Luisa Gelmi, Francesco Anastasi, Raffaella Bucci, Alessandro Contini, Donatella Nava, Gabriele Fontana, Fabio Usubelli, Meng Zhou","doi":"10.1002/ejoc.202401364","DOIUrl":"https://doi.org/10.1002/ejoc.202401364","url":null,"abstract":"A refresh and improvement of the well‐known myo‐inositol chemistry is reported here, setting up a new synthetic protocol to obtain orthogonally protected compounds, with a special focus on the preparation of 2‐O‐alkylated compounds. A gram scale synthesis of the 2‐allyl compound was performed and optimized in terms of yield. This intermediate is the precursor of chiro‐1‐inosose, for which synthetic procedures are lacking. Taking advantage of the easily handled allyl group, we were able to transform this keto compound into both the 1,2‐diketone and 3‐deoxy‐1,2‐diketone, intermediates of biological transformations used in several patented applications. Finally, to access poly‐hydroxylated‐(aminomethyl)cyclohexane compounds, the reaction of the keto compound with cyanide was optimized, affording cyanohydrins obtained as single stereoisomer, the precursor of the above compound.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"80 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435383","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jordan LEHOUX, Felix GROSJEAN, Alexandre LOBO, Michel LAGARDE, Nathalie Bernoud-Hubac, Thierry DURAND, Céline CRAUSTE
Docosahexaenoic acid (DHA, C22:6 n‐3) is a critical omega‐3 polyunsaturated fatty acid (PUFA) with essential roles in brain and retinal functions. Its selective uptake into these tissues is mediated by several pathways, including the transporter Mfsd2a, which preferentially utilizes lysophosphatidylcholine‐DHA (LPC‐DHA) as a substrate. Due to the low de novo synthesis of DHA, optimizing its dietary intake and exploring novel delivery strategies are important in pathologies that affect PUFA proportion. The present work focuses on developing an efficient chemo‐enzymatic methodology to access structured mixed DHA phosphatidylcholines (mixed DHA‐PCs), valuable biological tools for enhancing drug and/or DHA delivery to the brain and retina. Chemo‐enzymatic methods were established to synthesize mixed sn1‐ or sn2‐DHA‐PC isomers, to study the importance of DHA position, from cost‐effective glycerophosphorylcholine (GPC). The approach aligns with green chemistry principles by leveraging lipase‐catalyzed regioselective acylation and deacylation reactions, thus reducing the number of chemical steps compared to traditional methods. The resulting mixed PCs AceDoPC®, DoAcePC (stabilized forms of LPC‐DHA), and phenolic‐DHA‐PCs were produced at a scale suitable for future in vivo studies, enabling investigations into the positional effect of DHA on brain and retinal uptake.
{"title":"Chemo‐Enzymatic Synthesis of Mixed Docosahexaenoic Acid Phosphatidylcholine Conjugates","authors":"Jordan LEHOUX, Felix GROSJEAN, Alexandre LOBO, Michel LAGARDE, Nathalie Bernoud-Hubac, Thierry DURAND, Céline CRAUSTE","doi":"10.1002/ejoc.202500083","DOIUrl":"https://doi.org/10.1002/ejoc.202500083","url":null,"abstract":"Docosahexaenoic acid (DHA, C22:6 n‐3) is a critical omega‐3 polyunsaturated fatty acid (PUFA) with essential roles in brain and retinal functions. Its selective uptake into these tissues is mediated by several pathways, including the transporter Mfsd2a, which preferentially utilizes lysophosphatidylcholine‐DHA (LPC‐DHA) as a substrate. Due to the low de novo synthesis of DHA, optimizing its dietary intake and exploring novel delivery strategies are important in pathologies that affect PUFA proportion. The present work focuses on developing an efficient chemo‐enzymatic methodology to access structured mixed DHA phosphatidylcholines (mixed DHA‐PCs), valuable biological tools for enhancing drug and/or DHA delivery to the brain and retina. Chemo‐enzymatic methods were established to synthesize mixed sn1‐ or sn2‐DHA‐PC isomers, to study the importance of DHA position, from cost‐effective glycerophosphorylcholine (GPC). The approach aligns with green chemistry principles by leveraging lipase‐catalyzed regioselective acylation and deacylation reactions, thus reducing the number of chemical steps compared to traditional methods. The resulting mixed PCs AceDoPC®, DoAcePC (stabilized forms of LPC‐DHA), and phenolic‐DHA‐PCs were produced at a scale suitable for future in vivo studies, enabling investigations into the positional effect of DHA on brain and retinal uptake.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"16 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435405","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mohamed Ali Dridi, Mohamed Hasyeoui, Frédéric Lassagne, William Erb, Charline Piroud, Thomas Robert, Stéphane Bach, Ali Samarat, Soufiane Touil, Florence Mongin
Despite their potential in areas such as medicinal chemistry and organic materials, scaffolds in which quinoline and quinoxaline are fused to phosphacycles such as 1,3-oxaphosphole, 1,3-azaphosphole, P-arylated and P-alkoxylated 2,3-dihydro-1,3-azaphosphole P-oxides have, to our knowledge, never been reported. In this study we have developed a synthetic approach to [1,3]azaphospholo[4,5-f]quinolines and -quinoxalines from quinolin-6-amine and quinoxalin-6-amine. These were converted to 5-phosphanylquino(xa)lin-6-amines by regioselective iodination in position 5, cross-coupling with diethyl phosphite and reduction. Formation of the azaphosphole ring was then achieved by reaction with N,N-dimethylformamide dimethyl acetal. Attempts at C-H arylation in position 2 did not lead to the desired derivatives but rather to 1-arylated 2,3-dihydro-[1,3]azaphospholo[4,5-f]quino(xa)line 1-oxides. Access to 1-alkoxylated 2,3-dihydro-[1,3]azaphospholo[4,5-f]quinoline 1-oxides was also developed using as key steps cross-coupling with ethyl phosphinate formed in situ and the subsequent Kabachnik-Fields reaction. The resulting tricyclic compounds were finally tested against a panel of disease-related protein kinases.
{"title":"On the Synthesis of [1,3]Azaphospholo[4,5-f]quino(xa)lines and 2,3-Dihydro-[1,3]azaphospholo[4,5-f]quino(xa)line 1-oxides","authors":"Mohamed Ali Dridi, Mohamed Hasyeoui, Frédéric Lassagne, William Erb, Charline Piroud, Thomas Robert, Stéphane Bach, Ali Samarat, Soufiane Touil, Florence Mongin","doi":"10.1002/ejoc.202500080","DOIUrl":"https://doi.org/10.1002/ejoc.202500080","url":null,"abstract":"Despite their potential in areas such as medicinal chemistry and organic materials, scaffolds in which quinoline and quinoxaline are fused to phosphacycles such as 1,3-oxaphosphole, 1,3-azaphosphole, P-arylated and P-alkoxylated 2,3-dihydro-1,3-azaphosphole P-oxides have, to our knowledge, never been reported. In this study we have developed a synthetic approach to [1,3]azaphospholo[4,5-f]quinolines and -quinoxalines from quinolin-6-amine and quinoxalin-6-amine. These were converted to 5-phosphanylquino(xa)lin-6-amines by regioselective iodination in position 5, cross-coupling with diethyl phosphite and reduction. Formation of the azaphosphole ring was then achieved by reaction with N,N-dimethylformamide dimethyl acetal. Attempts at C-H arylation in position 2 did not lead to the desired derivatives but rather to 1-arylated 2,3-dihydro-[1,3]azaphospholo[4,5-f]quino(xa)line 1-oxides. Access to 1-alkoxylated 2,3-dihydro-[1,3]azaphospholo[4,5-f]quinoline 1-oxides was also developed using as key steps cross-coupling with ethyl phosphinate formed in situ and the subsequent Kabachnik-Fields reaction. The resulting tricyclic compounds were finally tested against a panel of disease-related protein kinases.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"4 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435569","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ExTTF derivatives (1–4) bearing aryl groups attached through sulfur bridges have been synthesized. The peripheral aryl groups have a certain influence on both the electronic and crystallographic properties of the exTTFs. Compounds 1–4 show two bands typical of exTTF derivatives near 360 and 430 nm. Compound 1 and 4 exhibit the characteristic electrochemical exTTF behavior, with one reversible two‐electron process ranging depending on their substitution the electron‐withdrawing ability. But 2 and 3 exhibit a similar single two‐electron oxidation wave but electrochemically irreversible redox with peak‐to‐peak potential separation. And 3 has a low redox potential, which is significantly inconsistent with the electron absorption of pyridine substituents. The crystal structures of 1–4 exhibit the characteristic butterfly shape. Moreover, the peripheral aryl groups exhibit multiple alignment modes with respect to the central exTTF core, caused by their rotation about the two C−S bonds of the sulfur bridges. Under the interaction of multiple molecules, exTTF shows different molecular packing structures. Compounds 1–4 have charge transfer with C60 due to their good electron‐donating ability, butterfly configuration, and free rotation of peripheral aryl groups. These results indicate that 1–4 organic electronic materials have potential applications in the field of supramolecular assembly.
{"title":"Synthesis, Structures, and Physical Properties of ExTTF Substituted with Aryl Groups through Sulfur Bridges and the Electron Transfers with C60","authors":"Longfei Ma , Lingxi Wu , Xiaofeng Lu","doi":"10.1002/ejoc.202401193","DOIUrl":"10.1002/ejoc.202401193","url":null,"abstract":"<div><div>ExTTF derivatives (<strong>1</strong>–<strong>4</strong>) bearing aryl groups attached through sulfur bridges have been synthesized. The peripheral aryl groups have a certain influence on both the electronic and crystallographic properties of the exTTFs. Compounds <strong>1</strong>–<strong>4</strong> show two bands typical of exTTF derivatives near 360 and 430 nm. Compound <strong>1</strong> and <strong>4</strong> exhibit the characteristic electrochemical exTTF behavior, with one reversible two‐electron process ranging depending on their substitution the electron‐withdrawing ability. But <strong>2</strong> and <strong>3</strong> exhibit a similar single two‐electron oxidation wave but electrochemically irreversible redox with peak‐to‐peak potential separation. And <strong>3</strong> has a low redox potential, which is significantly inconsistent with the electron absorption of pyridine substituents. The crystal structures of <strong>1</strong>–<strong>4</strong> exhibit the characteristic butterfly shape. Moreover, the peripheral aryl groups exhibit multiple alignment modes with respect to the central exTTF core, caused by their rotation about the two C−S bonds of the sulfur bridges. Under the interaction of multiple molecules, exTTF shows different molecular packing structures. Compounds <strong>1</strong>–<strong>4</strong> have charge transfer with C<sub>60</sub> due to their good electron‐donating ability, butterfly configuration, and free rotation of peripheral aryl groups. These results indicate that <strong>1</strong>–<strong>4</strong> organic electronic materials have potential applications in the field of supramolecular assembly.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"28 7","pages":"Article e202401193"},"PeriodicalIF":2.5,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142696860","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Joaquín Marchán‐García , Prof. Mariana Álvarez , Prof. Gabriel Radivoy , Prof. Yanina Moglie
A green and sustainable approach to the direct synthesis of thioesters has been developed using Fe3O4 as a low‐cost, easily prepared, reusable and environmentally safe catalyst. The cross dehydrogenative coupling (CDC) of various thiols and aldehydes in water, or even in the absence of solvent, using tert‐butylhydroperoxide as oxidant, under ligand and base‐free mild conditions, afforded the corresponding thioesters in good to excellent yields. This simple protocol features broad substrate scope, good compatibility with different functional groups, as well as high atom‐efficiency. The scalability, ease of (magnetic) recovery and reuse of the magnetite catalyst are additional eco‐friendly attributes of this methodology. Moreover, the broad synthetic applications of thioesters further highlight the potential utility of the present protocol.
{"title":"Magnetite: a Green, Sustainable and Recyclable Catalyst for Direct Synthesis of Thioesters by C−H Activation","authors":"Joaquín Marchán‐García , Prof. Mariana Álvarez , Prof. Gabriel Radivoy , Prof. Yanina Moglie","doi":"10.1002/ejoc.202400827","DOIUrl":"10.1002/ejoc.202400827","url":null,"abstract":"<div><div>A green and sustainable approach to the direct synthesis of thioesters has been developed using Fe<sub>3</sub>O<sub>4</sub> as a low‐cost, easily prepared, reusable and environmentally safe catalyst. The cross dehydrogenative coupling (CDC) of various thiols and aldehydes in water, or even in the absence of solvent, using <em>tert</em>‐butylhydroperoxide as oxidant, under ligand and base‐free mild conditions, afforded the corresponding thioesters in good to excellent yields. This simple protocol features broad substrate scope, good compatibility with different functional groups, as well as high atom‐efficiency. The scalability, ease of (magnetic) recovery and reuse of the magnetite catalyst are additional eco‐friendly attributes of this methodology. Moreover, the broad synthetic applications of thioesters further highlight the potential utility of the present protocol.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"28 7","pages":"Article e202400827"},"PeriodicalIF":2.5,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832394","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
High‐throughput experimentation was employed to discover p‐Anisil as a highly effective and versatile catalysts for the E‐to‐Z photoisomerization of cinnamic acid derivatives and other activated alkenes. This new catalytic system tolerated a number of functional groups found in medicinal chemistry. The discovery enabled the preparation of previously unknown complex Z‐alkenes in two steps directly from drugs or peptides.
采用高通量实验发现，对苯胺是肉桂酸衍生物和其他活化烯烃E - to - Z光异构化的高效和通用催化剂。这种新的催化体系可耐受药物化学中发现的许多官能团。这一发现使得直接从药物或多肽两步制备以前未知的Z -烯烃络合物成为可能。
{"title":"p‐Anisil as a Versatile Catalyst for the E‐to‐Z Photoisomerization of Activated Alkenes ‐ Application in Late‐Stage Modification of Small Molecule Drugs, Di‐ and Tripeptides","authors":"Thanh V. Q. Nguyen , Peter R. Hansen","doi":"10.1002/ejoc.202401338","DOIUrl":"10.1002/ejoc.202401338","url":null,"abstract":"<div><div>High‐throughput experimentation was employed to discover <em>p</em>‐Anisil as a highly effective and versatile catalysts for the <em>E‐to‐Z</em> photoisomerization of cinnamic acid derivatives and other activated alkenes. This new catalytic system tolerated a number of functional groups found in medicinal chemistry. The discovery enabled the preparation of previously unknown complex <em>Z</em>‐alkenes in two steps directly from drugs or peptides.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"28 7","pages":"Article e202401338"},"PeriodicalIF":2.5,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142815792","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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