Pedro Almendros, Daniel San Martín, Teresa Martínez del Campo
We report the direct and selective synthesis of oxadendralenes starting from readily available bis(α-hydroxyallenes). The designed sequence involves a hitherto unknown oxy-Cope rearrangement of allenols by supplying a site for the migration of the 1,2-diene moiety. Moreover, the so-prepared oxadendralenes were converted into valuable polyfunctionalized scaffolds through effective late-stage diversification.
{"title":"Synthesis of Oxadendralenes by Thermal Oxy-Cope Type Rearrangement of Bis(α-hydroxyallenes)","authors":"Pedro Almendros, Daniel San Martín, Teresa Martínez del Campo","doi":"10.1002/adsc.202500080","DOIUrl":"https://doi.org/10.1002/adsc.202500080","url":null,"abstract":"We report the direct and selective synthesis of oxadendralenes starting from readily available bis(α-hydroxyallenes). The designed sequence involves a hitherto unknown oxy-Cope rearrangement of allenols by supplying a site for the migration of the 1,2-diene moiety. Moreover, the so-prepared oxadendralenes were converted into valuable polyfunctionalized scaffolds through effective late-stage diversification.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"25 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462713","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}
Tulshiram Dadmal, Koppadi Syam Venkata Kishore, Chandrakant Wasekar, Prashant G. Borkar, Mangesh E. Shelke, sudhakar M bansod, Sunil Kumar Nechipadappu, P. Sathya Shanker
A facile one-pot, three-component cascade cyclization has been developed for synthesis of 2-trifluoromethyl-2-ol dihydropyrroles and 4-trifluoromethyl-4-ol dihydropyrroles from various substituted amines, 3-bromo-1,1,1-trifluoropropan-2-one, and substituted β-oxoamides using K₂CO₃ as an additive. This K₂CO₃-promoted method offers a simple and efficient approach for achieving highly regioselective products through cascade bond formation and cyclization. Post functionalization of resulting products into various valuable trifluoromethylated heterocycles including triazoles, isoxazoles, Mannich bases and the products from Sonogashira coupling reactions has also been reported. Additionally, a straightforward and scalable protocol for synthesis of 4-trifluoromethylpyrrole-3-carboxamide derivatives without K₂CO₃, utilizing diverse 1,3-dicarbonyl compounds has been established. This method demonstrates broad substrate compatibility, efficient tolerance towards a wide range of functional groups, making it a versatile strategy for accessing highly substituted trifluoromethylated pyrroles.
{"title":"One-pot tandem cyclization of β-oxoamides, primary amines, and 3-bromo-1,1,1-trifluoroacetone: Synthesis of 2/4-trifluoromethyl-substituted dihydropyrrol-2/4-ols","authors":"Tulshiram Dadmal, Koppadi Syam Venkata Kishore, Chandrakant Wasekar, Prashant G. Borkar, Mangesh E. Shelke, sudhakar M bansod, Sunil Kumar Nechipadappu, P. Sathya Shanker","doi":"10.1002/adsc.202401513","DOIUrl":"https://doi.org/10.1002/adsc.202401513","url":null,"abstract":"A facile one-pot, three-component cascade cyclization has been developed for synthesis of 2-trifluoromethyl-2-ol dihydropyrroles and 4-trifluoromethyl-4-ol dihydropyrroles from various substituted amines, 3-bromo-1,1,1-trifluoropropan-2-one, and substituted β-oxoamides using K₂CO₃ as an additive. This K₂CO₃-promoted method offers a simple and efficient approach for achieving highly regioselective products through cascade bond formation and cyclization. Post functionalization of resulting products into various valuable trifluoromethylated heterocycles including triazoles, isoxazoles, Mannich bases and the products from Sonogashira coupling reactions has also been reported. Additionally, a straightforward and scalable protocol for synthesis of 4-trifluoromethylpyrrole-3-carboxamide derivatives without K₂CO₃, utilizing diverse 1,3-dicarbonyl compounds has been established. This method demonstrates broad substrate compatibility, efficient tolerance towards a wide range of functional groups, making it a versatile strategy for accessing highly substituted trifluoromethylated pyrroles.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"22 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462712","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}
Jun Yang, Jianyu Zhang, Tianxing Li, Yunting Liu, Hui Jin, Do Hyun Ryu, Lixin Zhang
The Friedel-Crafts reaction between indoles and ketones poses a significant challenge. In this study, we developed an efficient and environmentally friendly approach for the synthesis of bis(indolyl)methanes bearing all-carbon quaternary and tertiary centers at room temperature under "on water" conditions. Notably, the utilization of saturated lithium chloride as a solvent greatly enhances the Brønsted acid-catalyzed double additions of indoles to ketones and aldehydes by promoting hydrophobic interactions. Additionally, LiCl acts as a Lewis acid catalyst for carbonyl activation and facilitates dehydration. This methodology demonstrates compatibility with various ketone substrates such as alkyl alkyl ketones and aryl alkyl ketones, along with aldehyde substrates. Furthermore, gram-scale productions were successful, and the LiCl solutions demonstrate reusability.
{"title":"Lithium Chloride-Promoted Brønsted Acid-Catalyzed Friedel-Crafts Alkylation Reaction of Indoles with Aldehydes and Ketones \"on Water\"","authors":"Jun Yang, Jianyu Zhang, Tianxing Li, Yunting Liu, Hui Jin, Do Hyun Ryu, Lixin Zhang","doi":"10.1002/adsc.202401542","DOIUrl":"https://doi.org/10.1002/adsc.202401542","url":null,"abstract":"The Friedel-Crafts reaction between indoles and ketones poses a significant challenge. In this study, we developed an efficient and environmentally friendly approach for the synthesis of bis(indolyl)methanes bearing all-carbon quaternary and tertiary centers at room temperature under \"on water\" conditions. Notably, the utilization of saturated lithium chloride as a solvent greatly enhances the Brønsted acid-catalyzed double additions of indoles to ketones and aldehydes by promoting hydrophobic interactions. Additionally, LiCl acts as a Lewis acid catalyst for carbonyl activation and facilitates dehydration. This methodology demonstrates compatibility with various ketone substrates such as alkyl alkyl ketones and aryl alkyl ketones, along with aldehyde substrates. Furthermore, gram-scale productions were successful, and the LiCl solutions demonstrate reusability.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"209 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462716","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}
A simple and efficient Ag‐catalyzed tandem selanylation/cyclization of o‐alkynyl benzylazides/o‐alkynyloxy benzylazides with diselenides has been developed. The reaction afforded a series of 3‐seleno‐8H‐[1,2,3]triazolo[5,1‐a]isoindoles and 3‐seleno‐4H,10H‐benzo[f][1,2,3]triazolo[5,1‐c][1,4]oxazepanes in moderate to good yields. The mechanistic study revealed that the intramolecular AAC reaction of an alkynyl selenium intermediate occurred. The synthesized compound 3k showed potent cancer cell‐growth inhibition activities.
{"title":"Silver‐mediated in‐situ generation of alkynyl selenium intramolecular AAC click reactions","authors":"Jian-Long Cao, Yi-Huan Zhou, Xi-Rui Gong, Mei-Lin Ren, Yan-yan Chen, Yan-Li Xu","doi":"10.1002/adsc.202500098","DOIUrl":"https://doi.org/10.1002/adsc.202500098","url":null,"abstract":"A simple and efficient Ag‐catalyzed tandem selanylation/cyclization of o‐alkynyl benzylazides/o‐alkynyloxy benzylazides with diselenides has been developed. The reaction afforded a series of 3‐seleno‐8H‐[1,2,3]triazolo[5,1‐a]isoindoles and 3‐seleno‐4H,10H‐benzo[f][1,2,3]triazolo[5,1‐c][1,4]oxazepanes in moderate to good yields. The mechanistic study revealed that the intramolecular AAC reaction of an alkynyl selenium intermediate occurred. The synthesized compound 3k showed potent cancer cell‐growth inhibition activities.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"198 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143443726","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}
The palladium/norbornene (Pd/NBE) cooperative catalysis, first identified by Catellani in 1997, provides an efficient approach for synthesizing highly functionalized aromatic compounds that are challenging to obtain through conventional methods. The developed synthetic approach integrates selective C‐H bond activation with sequential reactions, allowing for the targeted functionalization of both the ortho and ipso positions of aryl halides via aryl‐norbornadiene‐palladacycle (ANP), which in turn ensures high chemoselectivity and regioselectivity of the products. It is estimated that approximately 20% of all natural products are glycosylated, with the carbohydrates linked to these compounds frequently playing a critical role in their biological activity. Currently, research in carbohydrate chemistry predominantly concentrates on polysubstitutional derivatization or vicinal functionalization strategies. However, the limited availability of 1,2‐disubstituted compounds has been scarcely investigated, and previous studies often relied on directional group assistance to achieve disubstitution. Recently, significant advancements have been achieved with Pd/NBE cooperative catalysis, an area that has gained considerable importance in carbohydrate chemistry, presenting an opportunity to inspire further research interest in Catellani reactions. In this review, we provide a comprehensive analysis of the Pd/NBE strategy within the realm of sugar chemistry, encompass early research and advancement in catalytic reactions, outline synthetic potential, highlight the significant progress made, and emphasize the most recent developments and their applications in situ vicinal functionalization of carbohydrate derivatives.
{"title":"Palladium/Norbornene Cooperative Catalysis: A Modular In Situ Vicinal Functionalization Strategy for Recent Developments of Carbohydrate Chemistry","authors":"Himanshu Gangwar, Zanjila Azeem, Pintu Kumar Mandal","doi":"10.1002/adsc.202401570","DOIUrl":"https://doi.org/10.1002/adsc.202401570","url":null,"abstract":"The palladium/norbornene (Pd/NBE) cooperative catalysis, first identified by Catellani in 1997, provides an efficient approach for synthesizing highly functionalized aromatic compounds that are challenging to obtain through conventional methods. The developed synthetic approach integrates selective C‐H bond activation with sequential reactions, allowing for the targeted functionalization of both the ortho and ipso positions of aryl halides via aryl‐norbornadiene‐palladacycle (ANP), which in turn ensures high chemoselectivity and regioselectivity of the products. It is estimated that approximately 20% of all natural products are glycosylated, with the carbohydrates linked to these compounds frequently playing a critical role in their biological activity. Currently, research in carbohydrate chemistry predominantly concentrates on polysubstitutional derivatization or vicinal functionalization strategies. However, the limited availability of 1,2‐disubstituted compounds has been scarcely investigated, and previous studies often relied on directional group assistance to achieve disubstitution. Recently, significant advancements have been achieved with Pd/NBE cooperative catalysis, an area that has gained considerable importance in carbohydrate chemistry, presenting an opportunity to inspire further research interest in Catellani reactions. In this review, we provide a comprehensive analysis of the Pd/NBE strategy within the realm of sugar chemistry, encompass early research and advancement in catalytic reactions, outline synthetic potential, highlight the significant progress made, and emphasize the most recent developments and their applications in situ vicinal functionalization of carbohydrate derivatives.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"8 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435400","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}
This study investigates the visible‐light‐initiated uranyl(VI)‐catalyzed activation of Si−H bonds through direct hydrogen atom transfer, which facilitates the formation of silyl radicals from silanes. The silyl radical can abstract a chlorine atom from the sulfonyl chloride, leading to the generation of sulfonyl radicals. These silyl radicals and sulfonyl radicals could react with alkenes and alkynes, achieving the first example of uranyl‐catalyzed hydrosilylation and hydrosulfonylation of unsaturated C−C bonds. This method features mild reaction conditions and a broad substrate scope, and exhibits exceptional functional‐group tolerance. Consequently, it is suitable for the late‐stage functionalization of drug derivatives.
{"title":"Visible‐Light‐Initiated Uranyl‐Catalyzed Hydrosilylation and Hydrosulfonylation of Alkenes and Alkynes","authors":"Xingxing Gong , Qianyi Zhao , Congqing Zhu","doi":"10.1002/adsc.202400745","DOIUrl":"10.1002/adsc.202400745","url":null,"abstract":"<div><div>This study investigates the visible‐light‐initiated uranyl(VI)‐catalyzed activation of Si−H bonds through direct hydrogen atom transfer, which facilitates the formation of silyl radicals from silanes. The silyl radical can abstract a chlorine atom from the sulfonyl chloride, leading to the generation of sulfonyl radicals. These silyl radicals and sulfonyl radicals could react with alkenes and alkynes, achieving the first example of uranyl‐catalyzed hydrosilylation and hydrosulfonylation of unsaturated C−C bonds. This method features mild reaction conditions and a broad substrate scope, and exhibits exceptional functional‐group tolerance. Consequently, it is suitable for the late‐stage functionalization of drug derivatives.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 4","pages":"Article e202400745"},"PeriodicalIF":4.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142085311","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}
M. Trinidad Martín , Celia Maya , Agustín Galindo , M. Carmen Nicasio
We report the Ni‐catalyzed cyclotrimerization of terminal alkynes at very low loadings of catalysts (0.05 mol% for all substrates). The nickel catalyst containing a terphenyl phosphine ligand allows carrying out the reactions at room temperature in only 30 min, providing the arene products as a single regioisomer in most cases. The Ni complex is also competent for the synthesis of polysubstituted pyridines through the cycloadditions of diynes and nitriles at mild temperatures (25 ° or 50 °C) and low Ni loadings (1 mol%). Experimental data and computational studies support the involvement of monoligated PNi species in all fundamental steps of the catalytic cycle.
{"title":"Ni‐Catalyzed [2+2+2] Cycloaddition of Alkynes To Form Arenes and Pyridines at Low Catalyst Loadings","authors":"M. Trinidad Martín , Celia Maya , Agustín Galindo , M. Carmen Nicasio","doi":"10.1002/adsc.202400765","DOIUrl":"10.1002/adsc.202400765","url":null,"abstract":"<div><div>We report the Ni‐catalyzed cyclotrimerization of terminal alkynes at very low loadings of catalysts (0.05 mol% for all substrates). The nickel catalyst containing a terphenyl phosphine ligand allows carrying out the reactions at room temperature in only 30 min, providing the arene products as a single regioisomer in most cases. The Ni complex is also competent for the synthesis of polysubstituted pyridines through the cycloadditions of diynes and nitriles at mild temperatures (25 ° or 50 °C) and low Ni loadings (1 mol%). Experimental data and computational studies support the involvement of monoligated PNi species in all fundamental steps of the catalytic cycle.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 4","pages":"Article e202400765"},"PeriodicalIF":4.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/adsc.202400765","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398093","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Celeste Nobbio , William R. Birmingham , Elisabetta Brenna , Nicholas J. Turner , Davide Tessaro , Fabio Parmeggiani
Phenylalanine ammonia lyase (PAL) enzymes have been extensively exploited to produce differently substituted arylalanine analogues, but their use in the stereoselective synthesis of aliphatic fatty amino acids has never been addressed. In this work, a two‐step hydroamination‐hydrodesulfurisation process has been investigated for the production of aliphatic L‐α‐amino acids from thienylacrylic acids, easily accessible by condensation from the corresponding arylaldehydes. Wild‐type PALs from Planctomyces brasiliensis and Streptomyces rimosus were selected as the most promising candidates and improved by site‐directed mutagenesis, thus unlocking the hydroamination of a broad panel of 10 different thienylacrylic acids bearing aliphatic and aromatic substituents. The subsequent hydrodesulfurisation step, accomplished by means of inexpensive Raney nickel in mild conditions and aqueous medium, afforded the corresponding aliphatic α‐amino acids in 10–63% overall isolated yield and perfect enantiopurity. This chemo‐enzymatic process represents the first example of aliphatic amino acid production using PALs, circumventing a major limitation of those biocatalysts.
{"title":"Stereoselective Synthesis of Aliphatic α‐Amino Acids by Chemo‐Enzymatic Hydroamination‐Hydrodesulfurisation","authors":"Celeste Nobbio , William R. Birmingham , Elisabetta Brenna , Nicholas J. Turner , Davide Tessaro , Fabio Parmeggiani","doi":"10.1002/adsc.202401223","DOIUrl":"10.1002/adsc.202401223","url":null,"abstract":"<div><div>Phenylalanine ammonia lyase (PAL) enzymes have been extensively exploited to produce differently substituted arylalanine analogues, but their use in the stereoselective synthesis of aliphatic fatty amino acids has never been addressed. In this work, a two‐step hydroamination‐hydrodesulfurisation process has been investigated for the production of aliphatic L‐α‐amino acids from thienylacrylic acids, easily accessible by condensation from the corresponding arylaldehydes. Wild‐type PALs from <em>Planctomyces brasiliensis</em> and <em>Streptomyces rimosus</em> were selected as the most promising candidates and improved by site‐directed mutagenesis, thus unlocking the hydroamination of a broad panel of 10 different thienylacrylic acids bearing aliphatic and aromatic substituents. The subsequent hydrodesulfurisation step, accomplished by means of inexpensive Raney nickel in mild conditions and aqueous medium, afforded the corresponding aliphatic α‐amino acids in 10–63% overall isolated yield and perfect enantiopurity. This chemo‐enzymatic process represents the first example of aliphatic amino acid production using PALs, circumventing a major limitation of those biocatalysts.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 4","pages":"Article e202401223"},"PeriodicalIF":4.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/adsc.202401223","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793799","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ye Zhang , Zhoulu Wang , Min Ren , Xiaoxiang Zhang , Zhenqian Fu
A variety of structurally diverse spirocyclohexane oxindoles featuring a quaternary carbon centre have been successfully constructed through an N‐heterocyclic carbene‐catalyzed [4+2] annulation of isatin‐derived enals with α‐cyano‐β‐methylenones. This domino process exhibits a wide substrate tolerance, operates under mild conditions, and yields products with high enantioselectivities.
{"title":"N‐Heterocyclic Carbene‐Catalyzed Enantioselective Synthesis of Spirocyclohexane Oxindoles","authors":"Ye Zhang , Zhoulu Wang , Min Ren , Xiaoxiang Zhang , Zhenqian Fu","doi":"10.1002/adsc.202401205","DOIUrl":"10.1002/adsc.202401205","url":null,"abstract":"<div><div>A variety of structurally diverse spirocyclohexane oxindoles featuring a quaternary carbon centre have been successfully constructed through an N‐heterocyclic carbene‐catalyzed [4+2] annulation of isatin‐derived enals with <em>α</em>‐cyano‐<em>β</em>‐methylenones. This domino process exhibits a wide substrate tolerance, operates under mild conditions, and yields products with high enantioselectivities.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 4","pages":"Article e202401205"},"PeriodicalIF":4.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832611","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}
This is the report on the Lewis base catalysis of annulenones. Additionally, the synthesis of chiral annulenone catalysts and their application in asymmetric ring‐opening reactions of meso‐epoxides is shown. Annulenones, such as cyclopropenones and tropones, function as Lewis bases owing to their inherent polarity caused by aromaticity, resulting in the activation of silicon tetrachloride, which catalyzes the ring‐opening reaction of meso‐epoxides. Moreover, various chiral annulenone catalysts have been designed and synthesized, and microwave irradiation has been shown to improve the synthetic efficiency of chiral tropones. The chiral annulenones successfully catalyzed the asymmetric ring‐opening reaction of meso‐epoxides, resulting in the formation of 1,2‐chlorohydrins in a high yield and high enantioselectivity (up to 90% ee in 96% yield). These results represent the example of three‐ and seven‐membered annulenones as a chiral Lewis base catalyst.
{"title":"Three‐ and Seven‐membered Annulenones as a Lewis Base Catalyst for Enantioselective meso‐Epoxide Opening","authors":"Sachie Arae , Yasushi Shimoda , Mizuki Kuwajima , Shunsuke Kotani , Makoto Nakajima","doi":"10.1002/adsc.202401186","DOIUrl":"10.1002/adsc.202401186","url":null,"abstract":"<div><div>This is the report on the Lewis base catalysis of annulenones. Additionally, the synthesis of chiral annulenone catalysts and their application in asymmetric ring‐opening reactions of <em>meso</em>‐epoxides is shown. Annulenones, such as cyclopropenones and tropones, function as Lewis bases owing to their inherent polarity caused by aromaticity, resulting in the activation of silicon tetrachloride, which catalyzes the ring‐opening reaction of <em>meso</em>‐epoxides. Moreover, various chiral annulenone catalysts have been designed and synthesized, and microwave irradiation has been shown to improve the synthetic efficiency of chiral tropones. The chiral annulenones successfully catalyzed the asymmetric ring‐opening reaction of <em>meso</em>‐epoxides, resulting in the formation of 1,2‐chlorohydrins in a high yield and high enantioselectivity (up to 90% ee in 96% yield). These results represent the example of three‐ and seven‐membered annulenones as a chiral Lewis base catalyst.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 4","pages":"Article e202401186"},"PeriodicalIF":4.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142880025","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}
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