Wei Liu , Yeting Huang , Ziqiang Dai , Min Yu , Xuangan Liu , Weijun Yao , Xiaoyu Han
A methodology to access stereoisomeric sets of products bearing multiple stereogenic centers is still a significant challenge in asymmetric catalysis. We present herein our experimental studies on the stereodivergent synthesis of chiral hydrobenzofuran‐fused pyrrolidines with three stereogenic centers via organocatalytic asymmetric dearomative cyclization and epimerization process. Chiral bifunctional thiourea catalyst could successfully promote the enantioselective dearomatization cyclization of 2‐nitrobenzofurans with o‐hydroxy aromatic aldimines, which enabled the synthesis of (3S,3aR,8bR)‐hydrobenzofuran[3.2]pyrrolidines in 79–92% yields with >20:1 stereoselectivities and 93–>99% enantio‐selectivities. While catalytic amount of DBU could induce the direct intramolecular epimerization of (3S,3aR,8bR)‐hydrobenzofuran[3.2] pyrrolidines to its diastereomers (3R,3aR,8bR)‐hydrobenzofuran[3.2] pyrrolidines in 72–87% yields without loss of stereoselectivities. The mechanistic pathways of the epimerization process were investigated by a series of control experiments study. This work provides an alternative and forward solution for the stereodivergent preparation of functionalized pyrrolidines with potential bioactivities.
{"title":"Stereodivergent Synthesis of Chiral Hydrobenzofuranpyrrolidines by Catalytic Asymmetric Dearomative Cyclization and Controlled Epimerization","authors":"Wei Liu , Yeting Huang , Ziqiang Dai , Min Yu , Xuangan Liu , Weijun Yao , Xiaoyu Han","doi":"10.1002/adsc.202401194","DOIUrl":"10.1002/adsc.202401194","url":null,"abstract":"<div><div>A methodology to access stereoisomeric sets of products bearing multiple stereogenic centers is still a significant challenge in asymmetric catalysis. We present herein our experimental studies on the stereodivergent synthesis of chiral hydrobenzofuran‐fused pyrrolidines with three stereogenic centers via organocatalytic asymmetric dearomative cyclization and epimerization process. Chiral bifunctional thiourea catalyst could successfully promote the enantioselective dearomatization cyclization of 2‐nitrobenzofurans with <em>o</em>‐hydroxy aromatic aldimines, which enabled the synthesis of (3<em>S</em>,3a<em>R</em>,8b<em>R</em>)‐hydrobenzofuran[3.2]pyrrolidines in 79–92% yields with >20:1 stereoselectivities and 93–>99% enantio‐selectivities. While catalytic amount of DBU could induce the direct intramolecular epimerization of (3<em>S</em>,3a<em>R</em>,8b<em>R</em>)‐hydrobenzofuran[3.2] pyrrolidines to its diastereomers (3<em>R</em>,3a<em>R</em>,8b<em>R</em>)‐hydrobenzofuran[3.2] pyrrolidines in 72–87% yields without loss of stereoselectivities. The mechanistic pathways of the epimerization process were investigated by a series of control experiments study. This work provides an alternative and forward solution for the stereodivergent preparation of functionalized pyrrolidines with potential bioactivities.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 4","pages":"Article e202401194"},"PeriodicalIF":4.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486570","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}
Wangyu Li, Shiwen Zhou, He Tang, Fengjian Chu, Hongru Feng, Yuan-Jiang Pan
A convenient and efficient metal‐free protocol has been reported for formylation of various amines with carbon dioxide. This reaction could proceed under ambient conditions and show a broad substrate scope, encompassing primary amines, secondary amines, chiral amino acid esters and bioactive molecules. Furthermore, this method offers several advantages, including the preservation of substrate chirality, ease of separation and purification and the suitability of formic acid and formate salts as reactants in this reaction.
{"title":"A Mild Reductant NHC‐ligated Borane for N‑Formylation of Amines with CO2 under Ambient Conditions","authors":"Wangyu Li, Shiwen Zhou, He Tang, Fengjian Chu, Hongru Feng, Yuan-Jiang Pan","doi":"10.1002/adsc.202401384","DOIUrl":"https://doi.org/10.1002/adsc.202401384","url":null,"abstract":"A convenient and efficient metal‐free protocol has been reported for formylation of various amines with carbon dioxide. This reaction could proceed under ambient conditions and show a broad substrate scope, encompassing primary amines, secondary amines, chiral amino acid esters and bioactive molecules. Furthermore, this method offers several advantages, including the preservation of substrate chirality, ease of separation and purification and the suitability of formic acid and formate salts as reactants in this reaction.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"64 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418445","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}
We describe a novel cobalt/salicyloxazoline (Salox) catalytic system for enantioselective C‐H functionalization, enabling the synthesis of P‐stereogenic and axially chiral cyclic phosphinic amides. Chiral Salox ligands, conveniently prepared in a single step from salicylonitriles and chiral amino alcohols, facilitated this transformation with excellent enantioselectivities (92‐99% ee) and moderate to good yields (31 examples, 45‐89%). Mechanistic studies implicate a cobalt (III/IV/II) catalytic cycle in the C‐H annulation process, providing valuable insights into the stereoselective reaction pathway.
{"title":"Cobalt/Salox‐catalyzed Stereoselective C‐H Functionalization: Enantioselective Construction of Axially Chiral Cyclic Phosphinamides with P‐Stereogenic Center","authors":"Bo Jiang, Hui Wang, Xiaobin Sun, Yiyang Qiao, Xiufang Xu, Zhiwei Miao","doi":"10.1002/adsc.202500021","DOIUrl":"https://doi.org/10.1002/adsc.202500021","url":null,"abstract":"We describe a novel cobalt/salicyloxazoline (Salox) catalytic system for enantioselective C‐H functionalization, enabling the synthesis of P‐stereogenic and axially chiral cyclic phosphinic amides. Chiral Salox ligands, conveniently prepared in a single step from salicylonitriles and chiral amino alcohols, facilitated this transformation with excellent enantioselectivities (92‐99% ee) and moderate to good yields (31 examples, 45‐89%). Mechanistic studies implicate a cobalt (III/IV/II) catalytic cycle in the C‐H annulation process, providing valuable insights into the stereoselective reaction pathway.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"6 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393099","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}
Over the past two decades, iodine‐mediated free radical reactions have been extensively explored and employed in chemical transformations that complement traditional ionic reactions. In this review, we have updated the progress of the iodine‐mediated radical reactions in organic synthesis reported between 2015 and mid‐2024, and organized the reactions according to their mechanistic pathways. In general, the proposed mechanisms can be divided into four categories based on the radical initiation or its preceding steps, namely, (1) formation of a covalent X–I (X = C, N, S, Se) bond, which subsequently participates in a radical reaction; (2) formation of a noncovalent N•••I bond, which assists the homolyisis of the I–I bond; (3) formation of the key iodine radicals by visible‐light or heat induced homolysis of I2 or by electrochemical oxidation of iodide; (4) iodine induced peroxide decomposition via single electron transfer (SET) mechanism to generate alkoxy or alkyl peroxy radicals. We hope this review will provide readers with a comprehensive update on the iodine‐mediated radical reactions, thereby further inspiring more exciting advances in this emerging field.
{"title":"Recent Advances in Iodine‐Mediated Radical Reactions","authors":"Wen Yang, Jian Guo, Samual Hee, Yu Chen","doi":"10.1002/adsc.202401486","DOIUrl":"https://doi.org/10.1002/adsc.202401486","url":null,"abstract":"Over the past two decades, iodine‐mediated free radical reactions have been extensively explored and employed in chemical transformations that complement traditional ionic reactions. In this review, we have updated the progress of the iodine‐mediated radical reactions in organic synthesis reported between 2015 and mid‐2024, and organized the reactions according to their mechanistic pathways. In general, the proposed mechanisms can be divided into four categories based on the radical initiation or its preceding steps, namely, (1) formation of a covalent X–I (X = C, N, S, Se) bond, which subsequently participates in a radical reaction; (2) formation of a noncovalent N•••I bond, which assists the homolyisis of the I–I bond; (3) formation of the key iodine radicals by visible‐light or heat induced homolysis of I2 or by electrochemical oxidation of iodide; (4) iodine induced peroxide decomposition via single electron transfer (SET) mechanism to generate alkoxy or alkyl peroxy radicals. We hope this review will provide readers with a comprehensive update on the iodine‐mediated radical reactions, thereby further inspiring more exciting advances in this emerging field.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"30 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393098","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}
Sulfonyl fluoride compounds, particularly those with heterocyclic skeletons, have gained increasing attention due to their widespread applications in organic synthesis, drug discovery, and the life sciences. Consequently, the exploration of efficient and diverse approaches for synthesizing sulfonyl fluorides with heterocyclic skeletons has garnered significant interest from organic chemists. In recent years, great progress has been made in constructing sulfonyl fluorides with heterocyclic skeletons. This review comprehensively outlines the recent advancements in the construction of sulfonyl fluorides possessing heterocyclic skeletons via diverse routes. Additionally, it also highlights the challenges and opportunities concomitant with the synthesis of heterocyclic sulfonyl fluorides.
{"title":"Recent advancements in the synthesis of sulfonyl fluorides with heterocyclic skeletons","authors":"Yi-Chen Dong, Li-Jing Wang","doi":"10.1002/adsc.202401539","DOIUrl":"https://doi.org/10.1002/adsc.202401539","url":null,"abstract":"Sulfonyl fluoride compounds, particularly those with heterocyclic skeletons, have gained increasing attention due to their widespread applications in organic synthesis, drug discovery, and the life sciences. Consequently, the exploration of efficient and diverse approaches for synthesizing sulfonyl fluorides with heterocyclic skeletons has garnered significant interest from organic chemists. In recent years, great progress has been made in constructing sulfonyl fluorides with heterocyclic skeletons. This review comprehensively outlines the recent advancements in the construction of sulfonyl fluorides possessing heterocyclic skeletons via diverse routes. Additionally, it also highlights the challenges and opportunities concomitant with the synthesis of heterocyclic sulfonyl fluorides.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"9 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385274","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}
Yuchen Han, Nan Geng, Jiangtao Sha, Huanhuan Li, Chun You, Weidong Liu, Jie Zhang, Jianjun Shi, Xin Wu, Wuyuan Zhang
Heterocyclic scaffolds have broad applications in organic synthesis, resulting in the production of essential compounds utilized in pharmaceuticals, agrochemicals, and dietary products. In this study, we present the characterization of a discovered succinic semialdehyde dehydrogenase from Klebsiella pneumoniae (KpSSADH) and elucidate its crystallographic structure. Further investigation into the catalytic performance of KpSSADH reveals its remarkable efficiency in converting various heteroatomcontaining (including N, S, O, and their combinations) cyclic aldehydes into the corresponding acids with conversions reaching up to 99%. To expand the range of available substrates, we designed cascade reactions by integrating thiol oxidase from Methylovorus sp. MP688 or unspecific peroxygenase from Agrocybe aegerita with KpSSADH. Through this approach, the desired acids via alcohol oxidation and C-H bond oxyfunctionalization were obtained, respectively. The discovery of KpSSADH and the envisioned cascade reactions have significantly broadened the biocatalytic toolbox for synthesizing heteroatom-containing carboxylic acids, thereby holding potential for applications in the modern pharmaceutical industry.
{"title":"Aldehyde Dehydrogenase from Klebsiella pneumoniae: A Robust Biocatalyst for Preparing Heteroatom-Containing Carboxylic Acids","authors":"Yuchen Han, Nan Geng, Jiangtao Sha, Huanhuan Li, Chun You, Weidong Liu, Jie Zhang, Jianjun Shi, Xin Wu, Wuyuan Zhang","doi":"10.1002/adsc.202500027","DOIUrl":"https://doi.org/10.1002/adsc.202500027","url":null,"abstract":"Heterocyclic scaffolds have broad applications in organic synthesis, resulting in the\u0000production of essential compounds utilized in pharmaceuticals, agrochemicals, and\u0000dietary products. In this study, we present the characterization of a discovered succinic\u0000semialdehyde dehydrogenase from Klebsiella pneumoniae (KpSSADH) and elucidate\u0000its crystallographic structure. Further investigation into the catalytic performance of\u0000KpSSADH reveals its remarkable efficiency in converting various heteroatomcontaining\u0000(including N, S, O, and their combinations) cyclic aldehydes into the\u0000corresponding acids with conversions reaching up to 99%. To expand the range of\u0000available substrates, we designed cascade reactions by integrating thiol oxidase from\u0000Methylovorus sp. MP688 or unspecific peroxygenase from Agrocybe aegerita with\u0000KpSSADH. Through this approach, the desired acids via alcohol oxidation and C-H\u0000bond oxyfunctionalization were obtained, respectively. The discovery of KpSSADH and\u0000the envisioned cascade reactions have significantly broadened the biocatalytic toolbox\u0000for synthesizing heteroatom-containing carboxylic acids, thereby holding potential for\u0000applications in the modern pharmaceutical industry.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"54 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143371505","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}
Sofia Toldo, Lorenzo Poletti, Graziano Di Carmine, Olga Bortolini, Carmela De Risi, Simona Felletti, Greta Compagnin, Alessandro Massi, Daniele Ragno
A strategy for the immobilization of Johnston’s Mono(AMidine) catalyst (<b>MAM</b>) onto polystyrene, silica and hybrid silica-polystyrene nanoparticles is presented. The catalyst activity was evaluated in the stereoselective aza-Henry reaction leading to the pivotal β-amino nitroalkane precursors of the anti-cancer agents Nutlins (with Nutlin-3a as the most active drug). The effect of the support and the linker on the catalytic performance was investigated, observing an interesting match/mismatch effect when using a chiral linker. The polystyrene-supported 3-pyrrolidinol-linked <b>PS-(<i>S</i>)-Pyr-MAM</b> organocatalyst showed the best activity among the tested catalysts, behaving very similarly to the homogeneous counterpart in the synthesis of a library of Nutlins precursors: yield up to 95%, <i>ee</i> up to 99%, and dr up to >99:1. The catalyst recyclability was also assessed through simple filtration, yielding a satisfactory 93% <i>ee</i> after 5 cycles, showing only a moderate decrease in conversion efficiency (ca. 5% after each cycle), which resulted in an accumulated turnover number (TON) of 69.7.
{"title":"Effective and Practical Stereoselective Synthesis of Nutlins Precursors by Immobilization of Privileged Chiral Mono-Amidine Catalyst","authors":"Sofia Toldo, Lorenzo Poletti, Graziano Di Carmine, Olga Bortolini, Carmela De Risi, Simona Felletti, Greta Compagnin, Alessandro Massi, Daniele Ragno","doi":"10.1002/adsc.202500058","DOIUrl":"https://doi.org/10.1002/adsc.202500058","url":null,"abstract":"A strategy for the immobilization of Johnston’s Mono(AMidine) catalyst (<b>MAM</b>) onto polystyrene, silica and hybrid silica-polystyrene nanoparticles is presented. The catalyst activity was evaluated in the stereoselective aza-Henry reaction leading to the pivotal β-amino nitroalkane precursors of the anti-cancer agents Nutlins (with Nutlin-3a as the most active drug). The effect of the support and the linker on the catalytic performance was investigated, observing an interesting match/mismatch effect when using a chiral linker. The polystyrene-supported 3-pyrrolidinol-linked <b>PS-(<i>S</i>)-Pyr-MAM</b> organocatalyst showed the best activity among the tested catalysts, behaving very similarly to the homogeneous counterpart in the synthesis of a library of Nutlins precursors: yield up to 95%, <i>ee</i> up to 99%, and dr up to >99:1. The catalyst recyclability was also assessed through simple filtration, yielding a satisfactory 93% <i>ee</i> after 5 cycles, showing only a moderate decrease in conversion efficiency (ca. 5% after each cycle), which resulted in an accumulated turnover number (TON) of 69.7.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"57 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143371506","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}
Daniël S. Verdoorn, Alessio Zuliani, Prabhat Ranjan, Juan P. Holgado, Noureddine Khiar, Jordy Saya, Carolina Carrillo-Carrión, Bert Maes, Romano Orru
The synthesis of carbodiimides via nitrene transfer to isocyanides has garnered significant attention in recent years. However, this reaction predominantly relies on homogeneous catalytic systems with high catalyst loadings. In this study, we employed ZIF‐67 MOF as a heterogeneous catalyst for carbodiimide synthesis and conducted an in‐depth analysis of its stability. Our findings reveal the non‐innocent role of catalyst leaching, demonstrating that even as little as 0.04 mol% of leached cobalt species is sufficient to catalyze this reaction. This result is in contrast with previous reports, where 5–10 mol% of cobalt‐loading is required. Furthermore, this study highlights that lower catalyst loadings are more efficient, particularly in cases where isocyanides exhibit limited stability.
{"title":"Unveiling the Potential of a Cobalt‐Based Metal‐Organic Framework in Carbodiimide Synthesis","authors":"Daniël S. Verdoorn, Alessio Zuliani, Prabhat Ranjan, Juan P. Holgado, Noureddine Khiar, Jordy Saya, Carolina Carrillo-Carrión, Bert Maes, Romano Orru","doi":"10.1002/adsc.202401540","DOIUrl":"https://doi.org/10.1002/adsc.202401540","url":null,"abstract":"The synthesis of carbodiimides via nitrene transfer to isocyanides has garnered significant attention in recent years. However, this reaction predominantly relies on homogeneous catalytic systems with high catalyst loadings. In this study, we employed ZIF‐67 MOF as a heterogeneous catalyst for carbodiimide synthesis and conducted an in‐depth analysis of its stability. Our findings reveal the non‐innocent role of catalyst leaching, demonstrating that even as little as 0.04 mol% of leached cobalt species is sufficient to catalyze this reaction. This result is in contrast with previous reports, where 5–10 mol% of cobalt‐loading is required. Furthermore, this study highlights that lower catalyst loadings are more efficient, particularly in cases where isocyanides exhibit limited stability.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"20 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143192198","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}
Hao‐Yuan Li , Shen‐Zhen Zhang , Xiaoying Niu , Qing‐Yuan Meng , Xiu‐Long Yang
Here, we present a strategy for the visible‐light‐catalyzed synthesis of β‐lactams based on the Norrish type II reaction. This protocol uses acetonitrile as solvent and commercially available photocatalyst to drive the reaction. Notably, various challenging substrate types reported in previous studies undergo conversion. DFT calculations further elucidate the reaction mechanism, while discussing the competitiveness between [2+2] cycloaddition and the Norrish II reaction.
在此，我们介绍一种基于 Norrish II 型反应的可见光催化合成 β-内酰胺的策略。该方案使用乙腈作为溶剂，并使用市售光催化剂来驱动反应。值得注意的是，以往研究中报道的各种具有挑战性的底物类型都发生了转化。DFT 计算进一步阐明了反应机理，同时讨论了 [2+2] 环加成反应和 Norrish II 反应之间的竞争性。
{"title":"Visible Light Photocatalyzed Norrish Type II Reaction of Acrylamides for the Synthesis of β‐Lactams","authors":"Hao‐Yuan Li , Shen‐Zhen Zhang , Xiaoying Niu , Qing‐Yuan Meng , Xiu‐Long Yang","doi":"10.1002/adsc.202400976","DOIUrl":"10.1002/adsc.202400976","url":null,"abstract":"<div><div>Here, we present a strategy for the visible‐light‐catalyzed synthesis of <em>β</em>‐lactams based on the Norrish type II reaction. This protocol uses acetonitrile as solvent and commercially available photocatalyst to drive the reaction. Notably, various challenging substrate types reported in previous studies undergo conversion. DFT calculations further elucidate the reaction mechanism, while discussing the competitiveness between [2+2] cycloaddition and the Norrish II reaction.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 3","pages":"Article e202400976"},"PeriodicalIF":4.4,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142321932","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 S. Lamb , Moena Hirao , Noriyuki Suzuki , Masahiro Yoshizawa‐Fujita , Toyonobu Usuki , Yumiko Suzuki","doi":"10.1002/adsc.202400955","DOIUrl":"10.1002/adsc.202400955","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 3","pages":"Article e202400955"},"PeriodicalIF":4.4,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/adsc.202400955","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":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号