Herein, an electroreductive aryl radical enabled 5-exo-dig cyclization of N-cyano-2-halobenzamides is presented, providing a convenient route for the synthesis of a variety of 3-iminoisoindolin-1-ones in 30–75% yields. Simply by employing zinc plate instead of graphite rod anode, the products of the electrosynthesis are switched to diverse 3-aminoisoindolin-1-ones through aryl-radical-mediated 5-exo-dig cyclization and subsequent reductive hydrogenation. Furthermore, this anode material determined divergent 5-exo-dig cyclization features mild electrochemical conditions, excellent substrate scopes, and good functional group tolerance.
{"title":"Anode material determined divergent 5-exo-dig cyclization of N-cyano-2-halobenzamides toward 3-iminoisoindolin-1-ones and 3-aminoisoindolin-1-ones","authors":"Xiao-Qing Xie, Zi-Qiong Li, Wei Zhou, Chaozhihui Cheng, Jiang Bai, Haixin Ding, Xian-Rong Song, Mu-Jia Luo, qiang xiao","doi":"10.1002/adsc.202401276","DOIUrl":"https://doi.org/10.1002/adsc.202401276","url":null,"abstract":"Herein, an electroreductive aryl radical enabled 5-exo-dig cyclization of N-cyano-2-halobenzamides is presented, providing a convenient route for the synthesis of a variety of 3-iminoisoindolin-1-ones in 30–75% yields. Simply by employing zinc plate instead of graphite rod anode, the products of the electrosynthesis are switched to diverse 3-aminoisoindolin-1-ones through aryl-radical-mediated 5-exo-dig cyclization and subsequent reductive hydrogenation. Furthermore, this anode material determined divergent 5-exo-dig cyclization features mild electrochemical conditions, excellent substrate scopes, and good functional group tolerance.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"33 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589016","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}
Described herein is the discovery of a palladium-catalyzed chlorocylization strategy for the synthesis of 3‑chloroindoles tolerated with a wide range of functional groups in moderate to excellent yields. In this transformation, the solvent effect is so important that only THF presents the positive effect. Furthermore, the present method provides an essay access to the N-unprotected 3-chloroindoles. A mechanism study showed that 2-alkynlanilines were catalyzed by palladium to from corresponding indoles, followed by copper-mediated oxidation chlorination to deliver the 3-chloroindoles products.
{"title":"Synthesis of 3‑Chloroindoles via Palladium-Catalyzed Chlorocyclization of Unmasked 2‑Alkynylanilines","authors":"Yongpeng Zheng, Jianxiao Li, Wanqing Wu, Chaorong Qi, Huanfeng Jiang","doi":"10.1002/adsc.202401296","DOIUrl":"https://doi.org/10.1002/adsc.202401296","url":null,"abstract":"Described herein is the discovery of a palladium-catalyzed chlorocylization strategy for the synthesis of 3‑chloroindoles tolerated with a wide range of functional groups in moderate to excellent yields. In this transformation, the solvent effect is so important that only THF presents the positive effect. Furthermore, the present method provides an essay access to the N-unprotected 3-chloroindoles. A mechanism study showed that 2-alkynlanilines were catalyzed by palladium to from corresponding indoles, followed by copper-mediated oxidation chlorination to deliver the 3-chloroindoles products.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"87 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142579999","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}
Luca Nicchio, Lorenzo Di Terlizzi, luc Neuville, Maurizio Fagnoni, Stefano Protti, Géraldine Masson
We present a novel and highly efficient method for synthesizing polyfunctionalized 1,2,4-triazoles. This approach leverages visible light and arylazo sulfones in combination with N-vinyl amides, in the environmentally friendly solvent ethyl acetate. Remarkably, the reaction proceeds without the need for (photo)catalysts, ensuring near-perfect atom economy and producing only water as a by-product. This method exhibits excellent functional group tolerance and can be scaled for both batch and continuous-flow processes.
{"title":"Visible-Light Enabled Synthesis of 1-Aryl-3-Sulfonylmethyl-1,2,4-Triazoles by Arylazo Sulfones","authors":"Luca Nicchio, Lorenzo Di Terlizzi, luc Neuville, Maurizio Fagnoni, Stefano Protti, Géraldine Masson","doi":"10.1002/adsc.202401251","DOIUrl":"https://doi.org/10.1002/adsc.202401251","url":null,"abstract":"We present a novel and highly efficient method for synthesizing polyfunctionalized 1,2,4-triazoles. This approach leverages visible light and arylazo sulfones in combination with N-vinyl amides, in the environmentally friendly solvent ethyl acetate. Remarkably, the reaction proceeds without the need for (photo)catalysts, ensuring near-perfect atom economy and producing only water as a by-product. This method exhibits excellent functional group tolerance and can be scaled for both batch and continuous-flow processes.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"26 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142579876","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}
Li-Ning Chen, Shu-Nuo Liang, Juan Luo, Dan-Na Chen, Zhi-Peng Ye, Peng-Ju Xia
Herein, we introduce a novel method for the synthesis of S-substituted isothiourea compounds via the selective 1,2-carboimination between oxime esters as bifunctional reagents and the C=S bond of isothiocyanates under visible-light catalysis. This approach deviates from conventional methods by precisely modulating the substrate electronics to selectively functionalize the C=S bond of isothiocyanates over the C=N bond, eliminating the need for strong bases and high temperatures and bypassing the formation of thiourea intermediates. Consequently, this protocol enables the efficient one-step synthesis of S-alkyl isothioureas, with featuring mild reaction conditions, operational simplicity and broad substrate scope.
{"title":"Selective 1,2-Carboimination of Isothiocyanates to Access S-Substituted Isothioureas via Energy Transfer Catalysis","authors":"Li-Ning Chen, Shu-Nuo Liang, Juan Luo, Dan-Na Chen, Zhi-Peng Ye, Peng-Ju Xia","doi":"10.1002/adsc.202401233","DOIUrl":"https://doi.org/10.1002/adsc.202401233","url":null,"abstract":"Herein, we introduce a novel method for the synthesis of S-substituted isothiourea compounds via the selective 1,2-carboimination between oxime esters as bifunctional reagents and the C=S bond of isothiocyanates under visible-light catalysis. This approach deviates from conventional methods by precisely modulating the substrate electronics to selectively functionalize the C=S bond of isothiocyanates over the C=N bond, eliminating the need for strong bases and high temperatures and bypassing the formation of thiourea intermediates. Consequently, this protocol enables the efficient one-step synthesis of S-alkyl isothioureas, with featuring mild reaction conditions, operational simplicity and broad substrate scope.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"67 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580000","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 six-membered ring bromo-etherification of ε-alkenyl alcohols using <i>N</i>-oxide catalyst was developed to furnish 2-bromomethyl-6-substituted tetrahydropyrans with <i>cis</i>-selectivity and 3-bromomethyl isochromans in high yields. DFT calculations indicate that the NMO catalyst enhances the electrophilicity of the bromine atom on NBS via two hydrogen-bonding interactions after the formation of the NMO-NBS complex.
{"title":"N-Oxide-Catalyzed Six-Membered Ring Bromo-etherification of ε-Alkenyl Alcohols","authors":"Yuki Hoshino, Honoka Kasahara, Ryusei Marushima, Katsuhiko Moriyama","doi":"10.1002/adsc.202401209","DOIUrl":"https://doi.org/10.1002/adsc.202401209","url":null,"abstract":"A six-membered ring bromo-etherification of ε-alkenyl alcohols using <i>N</i>-oxide catalyst was developed to furnish 2-bromomethyl-6-substituted tetrahydropyrans with <i>cis</i>-selectivity and 3-bromomethyl isochromans in high yields. DFT calculations indicate that the NMO catalyst enhances the electrophilicity of the bromine atom on NBS via two hydrogen-bonding interactions after the formation of the NMO-NBS complex.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"48 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142574304","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}
Lijin Xu, Zhenni He, Ji Yang, Xiaohan Li, Wei Huang, Kai Liu, Qian Shi
The asymmetric transfer hydrogenation of various dibenzo-fused azepines including 5H-dibenzo[b,e][1,4]diazepines, dibenzo[b,f][1,4]thiazepines and 11H-dibenzo[b,e]azepines using chiral iridium diamine catalysts and HCO2H/NEt3 as the hydrogen source has been accomplished. A rang of chiral 10,11-dihydro-5H-dibenzo[b,e][1,4]diazepines, 10,11-dihydrodibenzo[b,f][1,4]thiazepine and 6,11-dihydro-5H-dibenzo[b,e]azepines have been prepared in 82-94% yields with 82-99% ee. Diversely substituted substrates are suitable for this transformation, and a number of functional groups are tolerated. The enantiocontrol is achieved via judicious choice of catalyst, additive and hydrogen source. The synthetic potential of this reaction is explored through gram-scale reactions without loss of reactivity and optical purity and further transformations on products.
{"title":"Iridium-Catalyzed Asymmetric Transfer Hydrogenation for Facile Access to Optically Active Dihydrodibenzo-Fused Azepines","authors":"Lijin Xu, Zhenni He, Ji Yang, Xiaohan Li, Wei Huang, Kai Liu, Qian Shi","doi":"10.1002/adsc.202401200","DOIUrl":"https://doi.org/10.1002/adsc.202401200","url":null,"abstract":"The asymmetric transfer hydrogenation of various dibenzo-fused azepines including 5H-dibenzo[b,e][1,4]diazepines, dibenzo[b,f][1,4]thiazepines and 11H-dibenzo[b,e]azepines using chiral iridium diamine catalysts and HCO2H/NEt3 as the hydrogen source has been accomplished. A rang of chiral 10,11-dihydro-5H-dibenzo[b,e][1,4]diazepines, 10,11-dihydrodibenzo[b,f][1,4]thiazepine and 6,11-dihydro-5H-dibenzo[b,e]azepines have been prepared in 82-94% yields with 82-99% ee. Diversely substituted substrates are suitable for this transformation, and a number of functional groups are tolerated. The enantiocontrol is achieved via judicious choice of catalyst, additive and hydrogen source. The synthetic potential of this reaction is explored through gram-scale reactions without loss of reactivity and optical purity and further transformations on products.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"54 12 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142574303","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}
Debora Schiroli, Aleksandr Voronov, Francesco Pancrazzi, Nunzio Iraci, Salvatore Vincenzo Giofré, Beatrice Macchi, Valeria Stefanizzi, Raffaella Mancuso, Bartolo Gabriele, Paolo Pio Mazzeo, Luca Capaldo, Nicola Della Ca'
Abstract. Additive carbonylations typically necessitate strong nucleophiles, such as alcohols or amines. In this study, we carbonylated a poorly nucleophilic urea, under oxidant-free conditions. Our straightforward carbonylative strategy enables access to versatile α,β-unsaturated γ-lactams featuring an aminocarbonyl fragment, utilizing readily available propargylic ureas as starting materials. The employment of the PdI2/KI catalytic system allowed complete regioselectivity (5-endo-dig), high functional group tolerance, broad substrate scope as well as operational simplicity (oxidant-free, organic ligand-free and base-free protocol). The synthetic utility of these γ-lactams is showcased through late-stage functionalizations, such as Giese reactions and peptide couplings.
{"title":"Direct Access to α,β-Unsaturated γ-Lactams via Palladium-Catalysed Carbonylation of Propargylic Ureas","authors":"Debora Schiroli, Aleksandr Voronov, Francesco Pancrazzi, Nunzio Iraci, Salvatore Vincenzo Giofré, Beatrice Macchi, Valeria Stefanizzi, Raffaella Mancuso, Bartolo Gabriele, Paolo Pio Mazzeo, Luca Capaldo, Nicola Della Ca'","doi":"10.1002/adsc.202401183","DOIUrl":"https://doi.org/10.1002/adsc.202401183","url":null,"abstract":"Abstract. Additive carbonylations typically necessitate strong nucleophiles, such as alcohols or amines. In this study, we carbonylated a poorly nucleophilic urea, under oxidant-free conditions. Our straightforward carbonylative strategy enables access to versatile α,β-unsaturated γ-lactams featuring an aminocarbonyl fragment, utilizing readily available propargylic ureas as starting materials. The employment of the PdI2/KI catalytic system allowed complete regioselectivity (5-endo-dig), high functional group tolerance, broad substrate scope as well as operational simplicity (oxidant-free, organic ligand-free and base-free protocol). The synthetic utility of these γ-lactams is showcased through late-stage functionalizations, such as Giese reactions and peptide couplings.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"241 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142574305","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}
Karthick Govindan, Chen Nian-Qi, Gokulakannan Venkatachalam, Tsz Fai Leung, Wei-Yu Lin
The selective N-C bond cleavage of amides to create value-added products through a transition metal-free approach has become a significant challenge. Here, we present a method to convert amides into N-(3-acylamidopropyl)lactams through sequential amide chemoselective N-C bond cleavage and amidine ring opening under mild conditions, applicable in batch and continuous flow processes. These methods utilize bench-stable reagents and are operationally straightforward and mild, enabling synthesis on a gram scale with excellent functional group tolerance. Additionally, the synthetic feasibility of these reactions under flow conditions has proven to be highly efficient, providing N-(3-acylamidopropyl)lactam derivatives with improved yields and shorter reaction time.
{"title":"Batch vs Continuous-Flow Method to Synthesize N-(3-acylamidopropyl)lactams through N-C Bond Cleavage in Amides with Amidines","authors":"Karthick Govindan, Chen Nian-Qi, Gokulakannan Venkatachalam, Tsz Fai Leung, Wei-Yu Lin","doi":"10.1002/adsc.202401179","DOIUrl":"https://doi.org/10.1002/adsc.202401179","url":null,"abstract":"The selective N-C bond cleavage of amides to create value-added products through a transition metal-free approach has become a significant challenge. Here, we present a method to convert amides into N-(3-acylamidopropyl)lactams through sequential amide chemoselective N-C bond cleavage and amidine ring opening under mild conditions, applicable in batch and continuous flow processes. These methods utilize bench-stable reagents and are operationally straightforward and mild, enabling synthesis on a gram scale with excellent functional group tolerance. Additionally, the synthetic feasibility of these reactions under flow conditions has proven to be highly efficient, providing N-(3-acylamidopropyl)lactam derivatives with improved yields and shorter reaction time.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"9 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142563218","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 photocatalytic methodology has been devised for the stereoselective construction of trisubstituted alkenes incorporating 3,3‐difluoro‐γ‐lactams in 17‐93% yields via a radical cascade process utilizing MBH acetates and N‐allylbromodifluoroacetamides as starting materials. The reaction mechanism involves single‐electron transfer, 5‐exo‐trig cyclization, radical addition, and elimination in a cascade fashion.
{"title":"Photo‐catalyzed Stereospecific Synthesis of Trisubstituted Alkenes Incorporating 3,3‐Difluoro‐γ‐Lactams from Morita‐Baylis‐Hillman Acetates and N‐Allylbromodifluoroacetamides","authors":"Jia-Yin Wang, Xi Chen, Chan Ai, Yu-Ting Wang, Hang-Dong Zuo, Jian-Wu Liu, Yue Zhang","doi":"10.1002/adsc.202401103","DOIUrl":"https://doi.org/10.1002/adsc.202401103","url":null,"abstract":"A photocatalytic methodology has been devised for the stereoselective construction of trisubstituted alkenes incorporating 3,3‐difluoro‐γ‐lactams in 17‐93% yields via a radical cascade process utilizing MBH acetates and N‐allylbromodifluoroacetamides as starting materials. The reaction mechanism involves single‐electron transfer, 5‐exo‐trig cyclization, radical addition, and elimination in a cascade fashion.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"6 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142561960","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}
Ines Kulašić, Nejc Petek, Helena Brodnik, Uroš Grošelj, Jurij Svete, Bogdan Štefane
The inside cover picture illustrates novel wavelength-dependent transformations of pyrazolo[1,2-a]pyrazolones into 3D-rich heterocyclic systems. The robot with flashlights represents how two distinct products can be easily obtained by simply adjusting the irradiation wavelength, leading to either 1,2-diazepines through ring expansion or tricyclic product via consecutive 4π-electrocyclization. These transformations are highly stereoselective, do not require photocatalysts or additives, and can be easily scaled up. For more details, see the Research Article by I. Kulašić, B. Štefane and co-workers (I. Kulašić, N. Petek, H. Brodnik, U. Grošelj, J. Svete, B. Štefane, Adv. Synth. Catal. 2024, 366, XXXX–XXXX; DOI: 10.1002/adsc.202400684)
{"title":"Photocatalyst-Free Wavelength-Dependant Sequential Ring Transformations of Pyrazolo[1,2-a]pyrazolones.","authors":"Ines Kulašić, Nejc Petek, Helena Brodnik, Uroš Grošelj, Jurij Svete, Bogdan Štefane","doi":"10.1002/adsc.202401227","DOIUrl":"https://doi.org/10.1002/adsc.202401227","url":null,"abstract":"The inside cover picture illustrates novel wavelength-dependent transformations of pyrazolo[1,2-<i>a</i>]pyrazolones into 3D-rich heterocyclic systems. The robot with flashlights represents how two distinct products can be easily obtained by simply adjusting the irradiation wavelength, leading to either 1,2-diazepines through ring expansion or tricyclic product via consecutive 4π-electrocyclization. These transformations are highly stereoselective, do not require photocatalysts or additives, and can be easily scaled up. For more details, see the Research Article by I. Kulašić, B. Štefane and co-workers (I. Kulašić, N. Petek, H. Brodnik, U. Grošelj, J. Svete, B. Štefane, <i>Adv. Synth. Catal</i>. <b>2024</b>, <i>366</i>, XXXX–XXXX; DOI: 10.1002/adsc.202400684)","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"16 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556057","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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