Wei Liu, Yeting Huang, Ziqiang Dai, Min Yu, Xuangan Liu, Weijun Yao, Xiaoyu Han
A rapid and straightforward way 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":"https://doi.org/10.1002/adsc.202401194","url":null,"abstract":"A rapid and straightforward way 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-\tselectivities. 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.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"12 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-21","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}
Electrosynthesis of selenylated-oxazolone derivatives via cascade selenylation/cyclization of ynamides was disclosed. A series of diaryl diselenides, dialkyl diselenides, and heteroaryl-substituted ynamides was tolerated in this protocol and delivered 4-selenyloxazolones in 28-83% yield. The scale-up reaction and the oxidation of selenylated-oxazolones was performed to showcase the practicability of this method. Furthermore, mechanistic experiments indicated that a cationic pathway instead of aradical pathway was probably involved.
{"title":"Electrochemical Synthesis of 4-Selenylated Oxazolones via Oxyselenylation of Ynamides","authors":"Jinhui Cai, Kaili Cen, Weishuang Li, Hongyi Lin, Haixia Zhang","doi":"10.1002/adsc.202401146","DOIUrl":"https://doi.org/10.1002/adsc.202401146","url":null,"abstract":"Electrosynthesis of selenylated-oxazolone derivatives via cascade selenylation/cyclization of ynamides was disclosed. A series of diaryl diselenides, dialkyl diselenides, and heteroaryl-substituted ynamides was tolerated in this protocol and delivered 4-selenyloxazolones in 28-83% yield. The scale-up reaction and the oxidation of selenylated-oxazolones was performed to showcase the practicability of this method. Furthermore, mechanistic experiments indicated that a cationic pathway instead of aradical pathway was probably involved.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"26 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142449651","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}
Thaís Rodrigues Arroio, Jan Philipp Nau, Kamil Hofman, Christoph Förster, Stephanie L. Faber, Sabine Becker, Katja Heinze, Giuliano Cesar Clososki, Georg Manolikakes
Abstract. Herein, we report a new approach for the light-mediated generation of sulfamoyl radicals using sulfur dioxide as key building block and the direct application of these radicals in the synthesis of sulfonamides. In the presence of different photoredox catalysts, sulfamoyl radicals can be generated directly from SO2 or the SO2 surrogate DABSO (1,4-diazabicyclo[2.2.2]octane·bis (sulfur dioxide) adduct) and N-aminopyridinium salts as nitrogen radical precursors. Trapping of the in situ generated sulfamoyl radicals with selected electron-rich olefins affords different sulfonamides in up to 86% yield in a three-component procedure. This transformation provides an attractive and complementary approach for the in situ generation of sulfamoyl radicals as synthetic intermediates for the assembly of the sulfonamide functionality, a motif in active pharmaceutical ingredients.
{"title":"Generation of Sulfamoyl Radicals via Visible-Light Mediated Fixation of Sulfur Dioxide for the Synthesis of Sulfonamides","authors":"Thaís Rodrigues Arroio, Jan Philipp Nau, Kamil Hofman, Christoph Förster, Stephanie L. Faber, Sabine Becker, Katja Heinze, Giuliano Cesar Clososki, Georg Manolikakes","doi":"10.1002/adsc.202401065","DOIUrl":"https://doi.org/10.1002/adsc.202401065","url":null,"abstract":"Abstract. Herein, we report a new approach for the light-mediated generation of sulfamoyl radicals using sulfur dioxide as key building block and the direct application of these radicals in the synthesis of sulfonamides. In the presence of different photoredox catalysts, sulfamoyl radicals can be generated directly from SO2 or the SO2 surrogate DABSO (1,4-diazabicyclo[2.2.2]octane·bis (sulfur dioxide) adduct) and N-aminopyridinium salts as nitrogen radical precursors. Trapping of the in situ generated sulfamoyl radicals with selected electron-rich olefins affords different sulfonamides in up to 86% yield in a three-component procedure. This transformation provides an attractive and complementary approach for the in situ generation of sulfamoyl radicals as synthetic intermediates for the assembly of the sulfonamide functionality, a motif in active pharmaceutical ingredients.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"43 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142449458","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This opinionated review underlines the increasing production of 1,3-propanediol (1,3-PDO) by whole cell biocatalytic fermentation of biomass and highlights how production has transitioned from petrochemicals to bio-renewables. Current uses of 1,3-PDO are listed. Some future prospects for evolving the current technology and expanding the chemical uses of 1,3-PDO use are discussed, with emphasis on catalytic and atom efficient chemistries. Lessons from the success of biomass derived 1,3-PDO are noted that may be applied to other bio-based organic platform chemicals.
{"title":"1,3-Propanediol, An Exemplary Bio-Renewable Organic Platform Chemical.","authors":"Andrew Marr","doi":"10.1002/adsc.202401066","DOIUrl":"https://doi.org/10.1002/adsc.202401066","url":null,"abstract":"This opinionated review underlines the increasing production of 1,3-propanediol (1,3-PDO) by whole cell biocatalytic fermentation of biomass and highlights how production has transitioned from petrochemicals to bio-renewables. Current uses of 1,3-PDO are listed. Some future prospects for evolving the current technology and expanding the chemical uses of 1,3-PDO use are discussed, with emphasis on catalytic and atom efficient chemistries. Lessons from the success of biomass derived 1,3-PDO are noted that may be applied to other bio-based organic platform chemicals.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"12 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142449433","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}
Eliška Mizerová, Martin Kos, Martin Jakubec, Marek Pavlica, Vladimír Církva, Jaroslav Zadny, Jan Storch, Tomáš Beránek
Recently developed synthetic protocols for the preparation of λ3-phosphanaphthalenes have broadened the general scope of organophosphorus chemistry, but a versatile protocol is still missing. Here, we describe a scalable synthetic approach for the construction of various substituted phosphanaphthalenes. We have obtained 11 derivatives through rigorous study and have demonstrated the robustness of this method. The optical properties of these phosphorus compounds and their aza and carbo analogues have been experimentally compared. Here, we show the power of the method in extending the synthesis to even larger polycyclic aromatic systems with embedded phosphine rings toward its potential applicability to materials science.
{"title":"Introduction of Phosphinine Ring into Aromatic Systems via Alkyne Cyclization","authors":"Eliška Mizerová, Martin Kos, Martin Jakubec, Marek Pavlica, Vladimír Církva, Jaroslav Zadny, Jan Storch, Tomáš Beránek","doi":"10.1002/adsc.202401203","DOIUrl":"https://doi.org/10.1002/adsc.202401203","url":null,"abstract":"Recently developed synthetic protocols for the preparation of λ3-phosphanaphthalenes have broadened the general scope of organophosphorus chemistry, but a versatile protocol is still missing. Here, we describe a scalable synthetic approach for the construction of various substituted phosphanaphthalenes. We have obtained 11 derivatives through rigorous study and have demonstrated the robustness of this method. The optical properties of these phosphorus compounds and their aza and carbo analogues have been experimentally compared. Here, we show the power of the method in extending the synthesis to even larger polycyclic aromatic systems with embedded phosphine rings toward its potential applicability to materials science.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"40 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142449459","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}
Al-Hajaj Hamood Al-Maani, Ahmad Takallou, Yazdanbakhsh Lotfi Nosood, Sulaiman Al-Shidhani, Mohammad Reza Hosseini, Muhammad Usman Anwar, Ahmed Al-Harrasi
The synthesis of indolizine derivatives was achieved through the reaction of pyridinium 1,4-zwitterionic thiolates with a diverse array of 2-methyl-2-nitro-3-aryloxiranes. Subsequent investigations unveiled a synthetic route to indolizines via a stepwise [(5 + 1) - 1] pathway, with unstable pyridothiazines serving as transient intermediates. DFT calculations elucidated that this transformation entails sequential annulation, deacylation, desulfurization, and oxidation steps.
{"title":"[(5 + 1) - 1] Cyclization of Nitroepoxides to Pyridinium 1,4-Zwitterionic Thiolates for the Synthesis of Indolizine Derivatives","authors":"Al-Hajaj Hamood Al-Maani, Ahmad Takallou, Yazdanbakhsh Lotfi Nosood, Sulaiman Al-Shidhani, Mohammad Reza Hosseini, Muhammad Usman Anwar, Ahmed Al-Harrasi","doi":"10.1002/adsc.202400961","DOIUrl":"https://doi.org/10.1002/adsc.202400961","url":null,"abstract":"The synthesis of indolizine derivatives was achieved through the reaction of pyridinium 1,4-zwitterionic thiolates with a diverse array of 2-methyl-2-nitro-3-aryloxiranes. Subsequent investigations unveiled a synthetic route to indolizines via a stepwise [(5 + 1) - 1] pathway, with unstable pyridothiazines serving as transient intermediates. DFT calculations elucidated that this transformation entails sequential annulation, deacylation, desulfurization, and oxidation steps.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"11 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142448151","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}
Imidazoheterocycles have extensive applications in the pharmaceutical industry and agrochemicals. A comprehensive overview has been provided on the current advancements in electrochemical functionalization, which has been classified ten different types of reactions. Electrochemical synthesis has emerged as a highly effective method for producing organic molecules, especially in the context of sustainable development. Employing electrons as the traceless oxidant, several C–H functionalization reactions of imidazo-fused heterocycles have been achieved at either the C3 or C5 positions. Electrons may serve as the reducing agent to synthesize pyridine rings that are either partially or fully saturated in imidazo[1,2-a]pyridines. The purpose of the review is to attract the interest of the scientific community and promote additional research on the functionalization of imidazoheterocycles using electrochemical methods.
{"title":"Recent Advances in the Electrochemical Functionalization of Imidazoheterocycles","authors":"Sifeng Li","doi":"10.1002/adsc.202401064","DOIUrl":"https://doi.org/10.1002/adsc.202401064","url":null,"abstract":"Imidazoheterocycles have extensive applications in the pharmaceutical industry and agrochemicals. A comprehensive overview has been provided on the current advancements in electrochemical functionalization, which has been classified ten different types of reactions. Electrochemical synthesis has emerged as a highly effective method for producing organic molecules, especially in the context of sustainable development. Employing electrons as the traceless oxidant, several C–H functionalization reactions of imidazo-fused heterocycles have been achieved at either the C3 or C5 positions. Electrons may serve as the reducing agent to synthesize pyridine rings that are either partially or fully saturated in imidazo[1,2-a]pyridines. The purpose of the review is to attract the interest of the scientific community and promote additional research on the functionalization of imidazoheterocycles using electrochemical methods.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"7 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142448113","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}
Amine compounds are widely found in natural products, pharmaceuticals, and pesticides. We propose a base-facilitated synthesis method of polysubstituted aromatic amines. A simple, rapid, plateau-utilization, and highly regioselective non-in-situ amination reaction was achieved by using aryl thianthrenium salt as the aryne precursor, and the arylynyl distortion induced by the substituents. This method provides new possibilities for organic synthesis.
{"title":"Thianthrenium salts to arynes: base promoted C-N bond construction","authors":"Jinghui Lyu, Xianghao Zhang, zijin Luo, Yang Jiang, Kexue Xing, guofu Zhang, Chengrong Ding","doi":"10.1002/adsc.202400889","DOIUrl":"https://doi.org/10.1002/adsc.202400889","url":null,"abstract":"Amine compounds are widely found in natural products, pharmaceuticals, and pesticides. We propose a base-facilitated synthesis method of polysubstituted aromatic amines. A simple, rapid, plateau-utilization, and highly regioselective non-in-situ amination reaction was achieved by using aryl thianthrenium salt as the aryne precursor, and the arylynyl distortion induced by the substituents. This method provides new possibilities for organic synthesis.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"98 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142448112","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}
Molybdenum catalysts bearing ONO, ON(N)O, ON(O)N and ON(S)O ligands were studied for catalytic deoxydehydration of vicinal diols. The complex bearing N',N'-bis(2-hydroxy-3,5-dimethylbenzyl)-N,N-dimethylethylenediamine ligand afforded full conversion and up to 97% selectivities towards alkenes, when aliphatic vicinal diols were subjected to the reaction at 5 mol% catalyst loading.
{"title":"Molybdenum-Catalysed Deoxydehydration: Transforming Linear Aliphatic 1,2-Diols into Terminal Alkenes","authors":"Normen Peulecke, Mahsa Sadeghi, Sergey Tin","doi":"10.1002/adsc.202400991","DOIUrl":"https://doi.org/10.1002/adsc.202400991","url":null,"abstract":"Molybdenum catalysts bearing ONO, ON(N)O, ON(O)N and ON(S)O ligands were studied for catalytic deoxydehydration of vicinal diols. The complex bearing N',N'-bis(2-hydroxy-3,5-dimethylbenzyl)-N,N-dimethylethylenediamine ligand afforded full conversion and up to 97% selectivities towards alkenes, when aliphatic vicinal diols were subjected to the reaction at 5 mol% catalyst loading.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"23 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142448213","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}
Hailin Liao, Mei Pan, Haicheng Zhao, Yuliang Qian, Jiyao Liu, Xiaoqin Liu, Liangce Rong
The iron (ІІІ)-promoted tandem cyclization of 1-(2-(allyloxy)aryl)-1H-indoles with diselenides has been developed for the preparation of seleno-benzo[2,3][1,4]oxazepino[4,5-a]indole derivatives. The investigation to determine the best reaction conditions indicated the use of 1-(2-(allyloxy)aryl)-1H-indoles (0.2 mmol) with diselenides (1.5 equiv) and iron(III) chloride (1.5 equiv) in acetonitrile at room temperature under air, and more than 40 examples were obtained. The reaction features access to selenized 7-membered containing nitrogen-oxygen heterocyclic skeleton, which also represents a 7-exo-trig cyclization process of 1-(2-((2-methylallyl)oxy)aryl)-1H-indoles and diselenides.
{"title":"Selenylation/Cyclization of 1-(2-(Allyloxy)aryl)-1H-indoles Access to Seleno-Benzo[2,3][1,4]oxazepino[4,5-a]indole Derivatives","authors":"Hailin Liao, Mei Pan, Haicheng Zhao, Yuliang Qian, Jiyao Liu, Xiaoqin Liu, Liangce Rong","doi":"10.1002/adsc.202401056","DOIUrl":"https://doi.org/10.1002/adsc.202401056","url":null,"abstract":"The iron (ІІІ)-promoted tandem cyclization of 1-(2-(allyloxy)aryl)-1H-indoles with diselenides has been developed for the preparation of seleno-benzo[2,3][1,4]oxazepino[4,5-a]indole derivatives. The investigation to determine the best reaction conditions indicated the use of 1-(2-(allyloxy)aryl)-1H-indoles (0.2 mmol) with diselenides (1.5 equiv) and iron(III) chloride (1.5 equiv) in acetonitrile at room temperature under air, and more than 40 examples were obtained. The reaction features access to selenized 7-membered containing nitrogen-oxygen heterocyclic skeleton, which also represents a 7-exo-trig cyclization process of 1-(2-((2-methylallyl)oxy)aryl)-1H-indoles and diselenides.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"31 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142440405","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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