The synthesis of β‐lactam scaffolds is of paramount importance due to their extensive applications in pharmaceuticals, particularly as antibiotics. Visible light photocatalysis has emerged as a revolutionary approach in this domain, providing a sustainable and efficient pathway for β‐lactam construction. In this review, we meticulously discuss the recent developments in the synthesis of photocatalysed β‐lactam frameworks.A key focus is the Staudinger reaction, traditionally a cornerstone in β‐lactam synthesis, and its adaptation to visible light photocatalysis. We explore the mechanistic intricacies of the Staudinger reaction under photochemical conditions, along with other pivotal cyclization strategies enabled by visible light. By illuminating the novel photocatalytic routes to β‐lactams, this review provides a thorough understanding of the state‐of‐the‐art techniques and sets the stage for future innovations in the green synthesis of these critical compounds.
{"title":"Photochemically Induced Approaches to the Syntheses of β‐Lactams","authors":"Vijay Das, Imtiaz Ahmed, Nikita Gupta, Ajit Gupta","doi":"10.1002/adsc.202400715","DOIUrl":"https://doi.org/10.1002/adsc.202400715","url":null,"abstract":"The synthesis of β‐lactam scaffolds is of paramount importance due to their extensive applications in pharmaceuticals, particularly as antibiotics. Visible light photocatalysis has emerged as a revolutionary approach in this domain, providing a sustainable and efficient pathway for β‐lactam construction. In this review, we meticulously discuss the recent developments in the synthesis of photocatalysed β‐lactam frameworks.A key focus is the Staudinger reaction, traditionally a cornerstone in β‐lactam synthesis, and its adaptation to visible light photocatalysis. We explore the mechanistic intricacies of the Staudinger reaction under photochemical conditions, along with other pivotal cyclization strategies enabled by visible light. By illuminating the novel photocatalytic routes to β‐lactams, this review provides a thorough understanding of the state‐of‐the‐art techniques and sets the stage for future innovations in the green synthesis of these critical compounds.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"206 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142384390","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}
Cristina Castanyer, Albert Artigas, Miquel Solà, Anna Pla-Quintana, Anna Roglans
The functionalization of fullerenes is important for several reasons, primarily related to enhancing their chemical reactivity, solubility, and potential of applications in optoelectronics and biomedicine. In this study, we present a novel approach to functionalize C60 through a cascade process encompassing an unprecedented Rh-catalyzed cycloisomerization of 1,6-allenynes to in situ generate a vinylallene that is followed by a Diels-Alder reaction with pristine fullerene, resulting in the formation of 6,6-fused bicyclic fullerene derivatives. The mechanism governing this process was elucidated by DFT calculations and confirmed by deuterium labelling and control experiments, demonstrating the critical role of traces of water in the reaction medium to mediate the observed reactivity.
{"title":"On the Functionalization of C60 with Vinylallenes Generated in situ by Rhodium Catalysis","authors":"Cristina Castanyer, Albert Artigas, Miquel Solà, Anna Pla-Quintana, Anna Roglans","doi":"10.1002/adsc.202401163","DOIUrl":"https://doi.org/10.1002/adsc.202401163","url":null,"abstract":"The functionalization of fullerenes is important for several reasons, primarily related to enhancing their chemical reactivity, solubility, and potential of applications in optoelectronics and biomedicine. In this study, we present a novel approach to functionalize C60 through a cascade process encompassing an unprecedented Rh-catalyzed cycloisomerization of 1,6-allenynes to in situ generate a vinylallene that is followed by a Diels-Alder reaction with pristine fullerene, resulting in the formation of 6,6-fused bicyclic fullerene derivatives. The mechanism governing this process was elucidated by DFT calculations and confirmed by deuterium labelling and control experiments, demonstrating the critical role of traces of water in the reaction medium to mediate the observed reactivity.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"7 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142379362","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 base-mediated cascade reaction of CF3-imidoyl sulfoxonium ylides (TFISYs) and diimides has been developed for the preparation of functionalized amidines. In the transformation, a cascade nucleophilic addition and subsequent [2,3]-sigmatropic rearrangement of sulfoxonium ylide occur to enable an intramolecular migration of dimethyl sulfoxide (DMSO). The unexpected result of the developed protocol demonstrates the chameleonic reactivity of TFISYs.
{"title":"Base-Mediated Cascade Reaction of CF3-Imidoyl Sulfoxonium Ylides and Diimides for the Synthesis of Functionalized Amidines","authors":"Sihao Ling, Qihua Chen, Zhengkai Chen","doi":"10.1002/adsc.202400996","DOIUrl":"https://doi.org/10.1002/adsc.202400996","url":null,"abstract":"A base-mediated cascade reaction of CF3-imidoyl sulfoxonium ylides (TFISYs) and diimides has been developed for the preparation of functionalized amidines. In the transformation, a cascade nucleophilic addition and subsequent [2,3]-sigmatropic rearrangement of sulfoxonium ylide occur to enable an intramolecular migration of dimethyl sulfoxide (DMSO). The unexpected result of the developed protocol demonstrates the chameleonic reactivity of TFISYs.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"224 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142383838","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}
With a number of biologically active members, 2-aroylchromones are valuable synthetic targets. A direct route towards 2-aroylchromones from 2-(methylsulfonyl)chromones and aldehydes via NHC-catalyzed C-C bond formation was developed. Yields of the synthesized 2-aroylchromones were up to 85%. Chromones with angioprotective or antibacterial properties were easily synthesized using the method developed. Additionally, the synthetic utility of the afforded chromones was demonstrated by using them to synthesize the anticancer compound wrightiadione and analogues of it.
{"title":"NHC-Catalyzed Synthesis of 2-Aroylchromones and Their Application in the Synthesis of Wrightiadione Analogues","authors":"Futa Koyama, Justin Lamb, Moena Hirao, Noriyuki Suzuki, Masahiro Yoshizawa-Fujita, Toyonobu Usuki, Yumiko Suzuki","doi":"10.1002/adsc.202400955","DOIUrl":"https://doi.org/10.1002/adsc.202400955","url":null,"abstract":"With a number of biologically active members, 2-aroylchromones are valuable synthetic targets. A direct route towards 2-aroylchromones from 2-(methylsulfonyl)chromones and aldehydes via NHC-catalyzed C-C bond formation was developed. Yields of the synthesized 2-aroylchromones were up to 85%. Chromones with angioprotective or antibacterial properties were easily synthesized using the method developed. Additionally, the synthetic utility of the afforded chromones was demonstrated by using them to synthesize the anticancer compound wrightiadione and analogues of it.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"223 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142374548","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}
Ruthenium-catalyzed and K2S2O8-mediated synthesis of diverse sulfonylated 5-aroyl-2-arylpyridines was developed through one-pot stepwise annulation of two molecules of β-ketosulfones and N,N-dimethylformamide (DMF) under the sealed tube conditions. In the overall process, DMF acts as the synthon of one carbon and one imino moiety in the construction of pyridine skeleton via cascade formation of single (C-C/C-N) and double (C=C/C=N) bonds under refluxing DMF conditions. Plausible reaction mechanism is proposed and discussed.
{"title":"One-pot Synthesis of Sulfonylated 5-Aroyl-2-arylpyridines via Ruthenium-Catalyzed and K2S2O8-Mediated Domino Annulation of β-Ketosulfones with DMF","authors":"Meng-Yang Chang, Chi-Ru Yang, Yeh-Long Chen","doi":"10.1002/adsc.202401116","DOIUrl":"https://doi.org/10.1002/adsc.202401116","url":null,"abstract":"Ruthenium-catalyzed and K2S2O8-mediated synthesis of diverse sulfonylated 5-aroyl-2-arylpyridines was developed through one-pot stepwise annulation of two molecules of β-ketosulfones and N,N-dimethylformamide (DMF) under the sealed tube conditions. In the overall process, DMF acts as the synthon of one carbon and one imino moiety in the construction of pyridine skeleton via cascade formation of single (C-C/C-N) and double (C=C/C=N) bonds under refluxing DMF conditions. Plausible reaction mechanism is proposed and discussed.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"13 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142374547","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}
Hua Huang, Xiao-Die An, Yi-Fan Wang, Yun-Xuan Tan, Ping Tian
Bicyclo[3.3.0]octanes represent crucial structural motifs found in various bioactive natural compounds. In this study, we present the first metal‐free formal [3 + 2] cycloadditions of alkyne‐tethered cyclopropyl ketones via pyridine‐boryl radical catalysis, affording bicyclo[3.3.0]octanes with high efficiency and broad substrate scope. This reaction features the generation of ketyl radical by pyridine‐boryl radical and a consecutive 5‐exo‐dig and 5‐exo‐trig radical cascade process.
{"title":"Pyridine‐Boryl Radical‐Catalyzed [3 + 2] Cycloadditions of Alkyne‐Tethered Cyclopropyl Ketones","authors":"Hua Huang, Xiao-Die An, Yi-Fan Wang, Yun-Xuan Tan, Ping Tian","doi":"10.1002/adsc.202401015","DOIUrl":"https://doi.org/10.1002/adsc.202401015","url":null,"abstract":"Bicyclo[3.3.0]octanes represent crucial structural motifs found in various bioactive natural compounds. In this study, we present the first metal‐free formal [3 + 2] cycloadditions of alkyne‐tethered cyclopropyl ketones via pyridine‐boryl radical catalysis, affording bicyclo[3.3.0]octanes with high efficiency and broad substrate scope. This reaction features the generation of ketyl radical by pyridine‐boryl radical and a consecutive 5‐exo‐dig and 5‐exo‐trig radical cascade process.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"63 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142374249","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}
Different catalysts are presented to overcome or augment a substrate’s innate regioselectivity. Rhodium was found to overcome the innate C3-selectivity <i>via</i> chelation-assisted rhodation. Conversely, palladium was found to enhance the innate C5-selectivity <i>via </i>electrophilic palladation. These reactions allow for the formation of a diverse range of synthetically versatile C3- and C5-alkynylated products from 2-pyridylthiophenes. Notably, this strategy was successfully employed in the straightforward synthesis of π-extended functionalized 2-pyridylthiophenes, which could be converted into more valuable compounds.
{"title":"Catalyst-Controlled Regiodivergent C–H Alkynylation of 2-Pyridylthiophenes","authors":"Yuting Gui, Yaokun Zhao, Xingchi Li, Taoyuan Liang, Shuangliang Zhao, Zhuan Zhang","doi":"10.1002/adsc.202400856","DOIUrl":"https://doi.org/10.1002/adsc.202400856","url":null,"abstract":"Different catalysts are presented to overcome or augment a substrate’s innate regioselectivity. Rhodium was found to overcome the innate C3-selectivity <i>via</i> chelation-assisted rhodation. Conversely, palladium was found to enhance the innate C5-selectivity <i>via </i>electrophilic palladation. These reactions allow for the formation of a diverse range of synthetically versatile C3- and C5-alkynylated products from 2-pyridylthiophenes. Notably, this strategy was successfully employed in the straightforward synthesis of π-extended functionalized 2-pyridylthiophenes, which could be converted into more valuable compounds.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"192 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142374470","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}
Delin Tang, Fang Zhang, Jinyun Luo, Zhihua Cai, Lin He, Guang-Fen Du
The cyclization reaction and hydrosulfonylation reaction of ynones have been simultaneously realized through a single operation. Under the mediation of cesium carbonate, different S-(α-hydroxyaryl) aryl thiosulfonates reacted with various ynones to produce functionalized vinyl sulfones in 37%-83% yields with E-selectivity. At the same time, a variety of benzoxathiins were formed in 42%-97% yields.
{"title":"Synthesis of Vinyl Sulfones and Benzoxathiins via Base-Catalyzed Reactions of o-Hydroxyaryl Thiosulfonates and Ynones","authors":"Delin Tang, Fang Zhang, Jinyun Luo, Zhihua Cai, Lin He, Guang-Fen Du","doi":"10.1002/adsc.202400456","DOIUrl":"https://doi.org/10.1002/adsc.202400456","url":null,"abstract":"The cyclization reaction and hydrosulfonylation reaction of ynones have been simultaneously realized through a single operation. Under the mediation of cesium carbonate, different S-(α-hydroxyaryl) aryl thiosulfonates reacted with various ynones to produce functionalized vinyl sulfones in 37%-83% yields with E-selectivity. At the same time, a variety of benzoxathiins were formed in 42%-97% yields.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"51 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142374469","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}
Herein, we reported the photocatalytic synthesis of 3‐silyl coumarins using hydrosilanes as the silyl radical source with aryl alkynoates. Readily prepared N‐aminopyridinium salts act as hydrogen atom transfer reagents for generating silyl radicals under photoredox catalysis. The reaction proceeds through silyl radical addition to alkyne followed by radical cascade cyclization/migration with subsequent oxidation and aromatization to give desired 3‐silyl coumarins in 34% to 89% yield.
{"title":"Photocatalytic Silylation of Aryl Alkynoates: Synthesis of Silylated Coumarins","authors":"Ravikumar Ladumor, Sourav Samanta, Sermadurai Selvakumar","doi":"10.1002/adsc.202401007","DOIUrl":"https://doi.org/10.1002/adsc.202401007","url":null,"abstract":"Herein, we reported the photocatalytic synthesis of 3‐silyl coumarins using hydrosilanes as the silyl radical source with aryl alkynoates. Readily prepared N‐aminopyridinium salts act as hydrogen atom transfer reagents for generating silyl radicals under photoredox catalysis. The reaction proceeds through silyl radical addition to alkyne followed by radical cascade cyclization/migration with subsequent oxidation and aromatization to give desired 3‐silyl coumarins in 34% to 89% yield.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"23 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142374472","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 visible-light-promoted, nitrogen-centered radical-initiated trifunctionalization of 5-hexenenitriles via diamidation and 1,4-cyano migration, using 1 mol% fac-Ir(ppy)₃ as the photoredox catalyst, is reported. In this protocol, the O-acylhydroxylamine derivative acts as a bifunctional reagent, and the carbonitrile solvent also participates in the reaction. This transformation proceeds at room temperature without the need for an external oxidant or reductant, yielding a wide range of functionalized β-amino nitriles, including the derivatives of natural products and pharmaceuticals.
{"title":"Visible-Light Photoredox-Catalyzed Trifunctionalization of Unactivated Alkenes via Diamidation and Cyano Migration","authors":"Abuthayir Mohamathu Ghouse, Bathula Maheswari, Srirama Murthy Akondi","doi":"10.1002/adsc.202400987","DOIUrl":"https://doi.org/10.1002/adsc.202400987","url":null,"abstract":"A visible-light-promoted, nitrogen-centered radical-initiated trifunctionalization of 5-hexenenitriles via diamidation and 1,4-cyano migration, using 1 mol% fac-Ir(ppy)₃ as the photoredox catalyst, is reported. In this protocol, the O-acylhydroxylamine derivative acts as a bifunctional reagent, and the carbonitrile solvent also participates in the reaction. This transformation proceeds at room temperature without the need for an external oxidant or reductant, yielding a wide range of functionalized β-amino nitriles, including the derivatives of natural products and pharmaceuticals.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"1 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142374450","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：