Feng Zhao, Fei Liu, Tongtong Shi, Ting Sun, Lianglong Sun, Si Chen, Xin Wang, Kai Sun
Herein, a novel visible-light-induced sulfonylation cyclization for the facile construction of challenging carbazole-fused eight-membered N-heterocycles has been described for the first time under additive-, base-, and external photosensitizer-free conditions. Mild reaction conditions, good functional group compatibility, and scalability reaction demonstrate the potential for further industrial application. A radical route was proposed based on radical inhibition experiments, visible-light irradiation on-off test, AQE calculation and fluorescence quenching studies.
{"title":"Visible-Light Induced Cyclization to Carbazole-Fused Eight-Membered Diazocan-5-ones","authors":"Feng Zhao, Fei Liu, Tongtong Shi, Ting Sun, Lianglong Sun, Si Chen, Xin Wang, Kai Sun","doi":"10.1002/adsc.202500322","DOIUrl":"https://doi.org/10.1002/adsc.202500322","url":null,"abstract":"Herein, a novel visible-light-induced sulfonylation cyclization for the facile construction of challenging carbazole-fused eight-membered N-heterocycles has been described for the first time under additive-, base-, and external photosensitizer-free conditions. Mild reaction conditions, good functional group compatibility, and scalability reaction demonstrate the potential for further industrial application. A radical route was proposed based on radical inhibition experiments, visible-light irradiation on-off test, AQE calculation and fluorescence quenching studies.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"67 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862520","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}
Maria Garcia Valverde, Javier Gómez-Ayuso, Israel Carreira-Barral, Roberto Quesada
Herein we present a novel one-por methodology for the synthesis of enantioenriched 2H-pyrrolespirosuccinimides by copper-catalyzed reactions on Ugi adducts derived from enantiopure α-alkylbenzyl amines through a chirality transfer process. We have proposed a mechanism supported by density functional theory (DFT) calculations, where a hydrogen radical-shuttle (HRS) process explains the chemical and stereochemical results. This work demonstrates the efficient stereoselective synthesis of structurally unique, highly functionalized nitrogen heterocyclic systems using simple protocols and affordable starting materials.
{"title":"Asymmetric synthesis of highly substituted spiro[2H-pyrrole-2,3-succinimide] derivatives by copper-catalyzed post-Ugi reactions","authors":"Maria Garcia Valverde, Javier Gómez-Ayuso, Israel Carreira-Barral, Roberto Quesada","doi":"10.1002/adsc.202500166","DOIUrl":"https://doi.org/10.1002/adsc.202500166","url":null,"abstract":"Herein we present a novel one-por methodology for the synthesis of enantioenriched 2H-pyrrolespirosuccinimides by copper-catalyzed reactions on Ugi adducts derived from enantiopure α-alkylbenzyl amines through a chirality transfer process. We have proposed a mechanism supported by density functional theory (DFT) calculations, where a hydrogen radical-shuttle (HRS) process explains the chemical and stereochemical results. This work demonstrates the efficient stereoselective synthesis of structurally unique, highly functionalized nitrogen heterocyclic systems using simple protocols and affordable starting materials.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"32 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862521","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}
Transition metal-catalyzed cascade cyclization of allenynes is regarded as an efficient approach for the synthesis of versatile cyclic frameworks. However, catalytic asymmetric cascade cyclizations of allenynes are still uncommon. Herein, we present the first cobalt-catalyzed enantioselective alkenylative cyclization of 1,6-allenynes with readily available alkenylboronic acids, providing five-membered carbo- and heterocycles with high efficiency (up to 97% yield), broad substrate scope, and moderate to good enantioselectivities (up to 95:5 er).
{"title":"Cobalt-Catalyzed Enantioselective Alkenylative Cyclization of 1,6-Allenynes","authors":"Tao Wang, Ji-Xun Guan, Yun-Xuan Tan, Ping Tian","doi":"10.1002/adsc.202500022","DOIUrl":"https://doi.org/10.1002/adsc.202500022","url":null,"abstract":"Transition metal-catalyzed cascade cyclization of allenynes is regarded as an efficient approach for the synthesis of versatile cyclic frameworks. However, catalytic asymmetric cascade cyclizations of allenynes are still uncommon. Herein, we present the first cobalt-catalyzed enantioselective alkenylative cyclization of 1,6-allenynes with readily available alkenylboronic acids, providing five-membered carbo- and heterocycles with high efficiency (up to 97% yield), broad substrate scope, and moderate to good enantioselectivities (up to 95:5 er).","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"38 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846453","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}
Methodology for direct fluoroalkenylation of phenolic OH function was developed using a fluorinated electrophilic reagent derived from HFO1234ze gas. Besides various functionalized phenols, tyrosine and tyrosine-based peptides were successfully conjugated under the optimized reaction conditions. Furthermore, the transformability of the fluoroalkenyl bromide motif was demonstrated to expand the space of bioconjugation via palladium catalyzed cross-coupling reactions.
{"title":"Development of Hydrofluoroolefin (HFO)-based direct O-fluoroalkenylation of phenols targeting tyrosine conjugation","authors":"Rihárd Sisa, Ferenc Béke, Zoltán Novák","doi":"10.1002/adsc.202500282","DOIUrl":"https://doi.org/10.1002/adsc.202500282","url":null,"abstract":"Methodology for direct fluoroalkenylation of phenolic OH function was developed using a fluorinated electrophilic reagent derived from HFO1234ze gas. Besides various functionalized phenols, tyrosine and tyrosine-based peptides were successfully conjugated under the optimized reaction conditions. Furthermore, the transformability of the fluoroalkenyl bromide motif was demonstrated to expand the space of bioconjugation via palladium catalyzed cross-coupling reactions.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"27 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143846544","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}
Dong-Sheng Li, Guang-Xu Zhang, Hao Qian, Fei Xue, Hong-Ping Deng
A mild, metal‐free protocol for cascade [4+2] addition‐defluorinative annulation of gem‐difluoroalkenes with alkynes was realized via photoredox catalysis. This method was feasible for a wide range of terminal alkynes, affording the 1,3‐cyclohexadiene derivatives or fluoro‐substituted arenes in moderate to good yields, respectively. The merit of this strategy was demonstrated by the late‐stage functionalization of pharmaceuticals and the synthesis of high‐value‐added complex molecules.
{"title":"Metal‐Free Divergent Photocatalytic Cascade [4+2] Addition‐Defluorinative Annulation of gem‐Difluoroalkenes with Terminal Alkynes","authors":"Dong-Sheng Li, Guang-Xu Zhang, Hao Qian, Fei Xue, Hong-Ping Deng","doi":"10.1002/adsc.202500314","DOIUrl":"https://doi.org/10.1002/adsc.202500314","url":null,"abstract":"A mild, metal‐free protocol for cascade [4+2] addition‐defluorinative annulation of gem‐difluoroalkenes with alkynes was realized via photoredox catalysis. This method was feasible for a wide range of terminal alkynes, affording the 1,3‐cyclohexadiene derivatives or fluoro‐substituted arenes in moderate to good yields, respectively. The merit of this strategy was demonstrated by the late‐stage functionalization of pharmaceuticals and the synthesis of high‐value‐added complex molecules.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"49 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143842112","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}
Gaochen Xu, Yongfang Wang, Yan Meng, Zheng Fang, Duan Jindian, Kai Guo
Transition metal-catalyzed or metal-free-mediated annulation of α,β-unsaturated ketoximes with unsaturated coupling partners has emerged as a powerful protocol for the assembly of diverse functionalized heterocycles, which is attributed to the ability of the oxime functionality to serve as a directing group for C−H activation, to undergo reductive N−O bond cleavage, and be activated by Lewis acids or reduced by iodide salts. In this review, we summarize the coupling reactions of three types of α,β-unsaturated ketoximes with various organic compounds containing unsaturated bonds such as alkenes, alkynes, carbonyls, nitriles and so on over the past decades. The reaction conditions, selected examples of the reaction scope, limitations, and reasonable mechanisms are critically described. Furthermore, the prospects for future challenges and opportunities are also explored.
{"title":"Recent Advances in Annulation Reactions of α,β-Unsaturated Ketoximes for the Synthesis of Structurally Diversified Heterocycles","authors":"Gaochen Xu, Yongfang Wang, Yan Meng, Zheng Fang, Duan Jindian, Kai Guo","doi":"10.1002/adsc.202500259","DOIUrl":"https://doi.org/10.1002/adsc.202500259","url":null,"abstract":"Transition metal-catalyzed or metal-free-mediated annulation of α,β-unsaturated ketoximes with unsaturated coupling partners has emerged as a powerful protocol for the assembly of diverse functionalized heterocycles, which is attributed to the ability of the oxime functionality to serve as a directing group for C−H activation, to undergo reductive N−O bond cleavage, and be activated by Lewis acids or reduced by iodide salts. In this review, we summarize the coupling reactions of three types of α,β-unsaturated ketoximes with various organic compounds containing unsaturated bonds such as alkenes, alkynes, carbonyls, nitriles and so on over the past decades. The reaction conditions, selected examples of the reaction scope, limitations, and reasonable mechanisms are critically described. Furthermore, the prospects for future challenges and opportunities are also explored.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"29 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143842104","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}
Davide Castiglione, Margherita Miele, Alberto Nardi, Laura Castoldi, Vittorio Pace
The hitherto few explored α‐halomethyl amidine motif has been assembled through the addition of a lithiated (di)‐halomethane (i.e. carbenoid) to easily accessible N,N’‐diaryl substituted carbodiimides. Despite the inherent low electrophilicity of these heterocumulenes – as quantitatively determined in Mayr’s previous studies – their sp‐hybridized carbon atom acts as a competent site of attack for these tamed nucleophiles. The overall high‐yielding transformation featuring a genuine chemoselective profile – as documented by employing variously functionalized materials – is adaptable to the addition of dihalogenated carbenoids. Reaction products could be advantageously employed in nucleophilic substitution sequences, as well as, in further functionalization of the nitrogen atoms due to the constitutive heteroallyl‐type skeleton.
{"title":"Chemoselective Synthesis of α‐Chloro and α,α ‐Dichloro acetamidines via the Carbenoids Addition to Inherently Low Electrophilic Carbodiimides","authors":"Davide Castiglione, Margherita Miele, Alberto Nardi, Laura Castoldi, Vittorio Pace","doi":"10.1002/adsc.202500320","DOIUrl":"https://doi.org/10.1002/adsc.202500320","url":null,"abstract":"The hitherto few explored α‐halomethyl amidine motif has been assembled through the addition of a lithiated (di)‐halomethane (i.e. carbenoid) to easily accessible N,N’‐diaryl substituted carbodiimides. Despite the inherent low electrophilicity of these heterocumulenes – as quantitatively determined in Mayr’s previous studies – their sp‐hybridized carbon atom acts as a competent site of attack for these tamed nucleophiles. The overall high‐yielding transformation featuring a genuine chemoselective profile – as documented by employing variously functionalized materials – is adaptable to the addition of dihalogenated carbenoids. Reaction products could be advantageously employed in nucleophilic substitution sequences, as well as, in further functionalization of the nitrogen atoms due to the constitutive heteroallyl‐type skeleton.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"6 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143842125","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}
Homogeneous transition-metal-catalyzed alkyne cascade cyclization reaction has attracted much attentions over the past decades. However, the relevant homogeneous transition-metal-catalyzed cyclization of allenynes has seldom been explored probably due to noticeable chemo-, regio-, and stereoselectivity. Described herein is an efficient homogeneous copper-catalyzed cycloisomerization reaction of allenynes, thus leading to a practical and atom-economic access to an array of valuable functionalized pyrroles by formal [3 + 2] cycloaddition via Cu-containing all-carbon 1,4-dipoles.
{"title":"Homogeneous Copper-Catalyzed Cycloisomerization Reaction of Allenynes: Rapid Access to Functionalized Pyrroles","authors":"Kua-Fei Wei, Xiu-Hong Zhu, Guang-Xin Ru, Wen-Bo Shen","doi":"10.1002/adsc.202500303","DOIUrl":"https://doi.org/10.1002/adsc.202500303","url":null,"abstract":"Homogeneous transition-metal-catalyzed alkyne cascade cyclization reaction has attracted much attentions over the past decades. However, the relevant homogeneous transition-metal-catalyzed cyclization of allenynes has seldom been explored probably due to noticeable chemo-, regio-, and stereoselectivity. Described herein is an efficient homogeneous copper-catalyzed cycloisomerization reaction of allenynes, thus leading to a practical and atom-economic access to an array of valuable functionalized pyrroles by formal [3 + 2] cycloaddition via Cu-containing all-carbon 1,4-dipoles.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"7 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832189","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}
Pd-catalyzed reactions are among the most straightforward and efficient methods to proficiently build Csp2-Csp2 bonds. Nevertheless, thermal activation remains mandatory in most cases, which may decrease the compatibility with sensitive functional groups. In this context, improvements of conventional strategies must be an important source of research in order to enhance the applicability of such methods for building complex scaffolds. In this work, we contribute to this aim by implying visible-light as the sole energy source in a Pd-catalyzed rearrangement reaction involving N-tosylhydrazones and aryl halides. These mild reaction conditions efficiently allow oxidative addition, aryl migration and β-hydride elimination at room temperature, allowing the construction of various 1,1’ disubstituted olefins.
{"title":"Illuminating the Path of Rearrangement: Visible Light-Driven Pd-Catalyzed Substituted Olefins Synthesis","authors":"jenifer Sharshonov, Valentin Duchemann, Yuqian Sun, Christine Tran, Philippe Belmont, Abdallah HAMZE, Diana Lamaa, Etienne BRACHET","doi":"10.1002/adsc.202500161","DOIUrl":"https://doi.org/10.1002/adsc.202500161","url":null,"abstract":"Pd-catalyzed reactions are among the most straightforward and efficient methods to proficiently build Csp2-Csp2 bonds. Nevertheless, thermal activation remains mandatory in most cases, which may decrease the compatibility with sensitive functional groups. In this context, improvements of conventional strategies must be an important source of research in order to enhance the applicability of such methods for building complex scaffolds. In this work, we contribute to this aim by implying visible-light as the sole energy source in a Pd-catalyzed rearrangement reaction involving N-tosylhydrazones and aryl halides. These mild reaction conditions efficiently allow oxidative addition, aryl migration and β-hydride elimination at room temperature, allowing the construction of various 1,1’ disubstituted olefins.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"23 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832190","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}
Lidia Prieto, Marcos Escolano, Daniel Gaviña, Luis Paredes-Soler, Santiago Díaz Oltra, Maria Sanchez-Rosello, Carlos del Pozo
A new family of fluorinated dihydropyrrolizinones has been synthesized starting from fluorinated enamino amides and aliphatic conjugated ketones. The reaction comprises a cross metathesis reaction followed by a tandem cycloaromatization/ enamine hydrolysis/ intramolecular Friedel-Crafts alkylation sequence. This pot-economical process takes place in good yields (35-67%), taking into account that it consists of four consecutive reactions. Aromatic enones are also good partners for this protocol although, in this case, the cross metathesis reaction has to be performed in a separated step.
{"title":"Pot-Economical Synthesis of Fluorinated Pyrrolizinone Derivatives","authors":"Lidia Prieto, Marcos Escolano, Daniel Gaviña, Luis Paredes-Soler, Santiago Díaz Oltra, Maria Sanchez-Rosello, Carlos del Pozo","doi":"10.1002/adsc.202500209","DOIUrl":"https://doi.org/10.1002/adsc.202500209","url":null,"abstract":"A new family of fluorinated dihydropyrrolizinones has been synthesized starting from fluorinated enamino amides and aliphatic conjugated ketones. The reaction comprises a cross metathesis reaction followed by a tandem cycloaromatization/ enamine hydrolysis/ intramolecular Friedel-Crafts alkylation sequence. This pot-economical process takes place in good yields (35-67%), taking into account that it consists of four consecutive reactions. Aromatic enones are also good partners for this protocol although, in this case, the cross metathesis reaction has to be performed in a separated step.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"76 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832188","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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