Pub Date : 2024-02-06DOI: 10.24820/ark.5550190.p012.140
Gilles Hanquet, Loic Jeanmart, Kalina Mambourg, Steve Lanners
We dedicate this work to Professor Léon Ghosez, an inspiring mentor, in recognition of his important contributions to organic synthesis
我们将这部作品献给鼓舞人心的导师 Léon Ghosez 教授，以表彰他对有机合成做出的重要贡献
{"title":"The Diels-Alder reaction of 1,4-quinones in hexafluoroisopropanol","authors":"Gilles Hanquet, Loic Jeanmart, Kalina Mambourg, Steve Lanners","doi":"10.24820/ark.5550190.p012.140","DOIUrl":"https://doi.org/10.24820/ark.5550190.p012.140","url":null,"abstract":"We dedicate this work to Professor Léon Ghosez, an inspiring mentor, in recognition of his important contributions to organic synthesis","PeriodicalId":8432,"journal":{"name":"Arkivoc","volume":null,"pages":null},"PeriodicalIF":0.9,"publicationDate":"2024-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139683053","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-02-01DOI: 10.24820/ark.5550190.p012.131
K. Maruoka, Shiyong Liu, Zhe Wang, Terumasa Kato, Yan Liu
Organophosphorus compounds are among the most fundamental and versatile bioactive molecules in medicinal and agricultural fields. Phosphonate (R 1 P(=O)(OR 2 )) compounds, in particular, are garnering considerable attention as prodrugs. Herein transition-metal-catalyzed C – P cross-coupling reaction between P(O) – H compounds and a series of alkylsilyl peroxides as alkyl radical precursors is reported. The reaction proceeded under mild conditions and various coupling products were synthesized from the corresponding dialkyl phosphonates and diarylphosphine oxides using copper and nickel catalysts. Mechanistic studies suggested that a silyl group is necessary to obtain the desired coupling products from dialkyl phosphonates under mild conditions.
有机磷化合物是医药和农业领域最基本、用途最广泛的生物活性分子之一。膦酸盐（R 1 P(=O)(OR 2 )）化合物作为原药尤其受到广泛关注。本文报告了在过渡金属催化下，P(O) - H 化合物与一系列作为烷基自由基前体的烷基硅基过氧化物之间发生的 C - P 交叉偶联反应。该反应在温和的条件下进行，并利用铜和镍催化剂从相应的二烷基膦酸盐和二元膦氧化物中合成了各种偶联产物。机理研究表明，要在温和条件下从二烷基膦酸盐中获得所需的偶联产物，必须要有硅烷基。
{"title":"Copper- and nickel- catalyzed C–P coupling reactions between P(O)–H compounds and alkyl radicals generated from alkylsilyl peroxides","authors":"K. Maruoka, Shiyong Liu, Zhe Wang, Terumasa Kato, Yan Liu","doi":"10.24820/ark.5550190.p012.131","DOIUrl":"https://doi.org/10.24820/ark.5550190.p012.131","url":null,"abstract":"Organophosphorus compounds are among the most fundamental and versatile bioactive molecules in medicinal and agricultural fields. Phosphonate (R 1 P(=O)(OR 2 )) compounds, in particular, are garnering considerable attention as prodrugs. Herein transition-metal-catalyzed C – P cross-coupling reaction between P(O) – H compounds and a series of alkylsilyl peroxides as alkyl radical precursors is reported. The reaction proceeded under mild conditions and various coupling products were synthesized from the corresponding dialkyl phosphonates and diarylphosphine oxides using copper and nickel catalysts. Mechanistic studies suggested that a silyl group is necessary to obtain the desired coupling products from dialkyl phosphonates under mild conditions.","PeriodicalId":8432,"journal":{"name":"Arkivoc","volume":null,"pages":null},"PeriodicalIF":0.9,"publicationDate":"2024-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139686850","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-01-17DOI: 10.24820/ark.5550190.p012.138
Ahmed H. M. Elwahy, Hadeel F. Hammad, Ahmed F. Darweesh, M. A. Abdelaziz, Ismail A. Abdelhamid
{"title":"2-Oxo-2-(arylamino)ethyl 4-formylbenzoates: Versatile precursors for the Synthesis of novel fused dihydropyrans linked to ester and amide groups through Michael reaction","authors":"Ahmed H. M. Elwahy, Hadeel F. Hammad, Ahmed F. Darweesh, M. A. Abdelaziz, Ismail A. Abdelhamid","doi":"10.24820/ark.5550190.p012.138","DOIUrl":"https://doi.org/10.24820/ark.5550190.p012.138","url":null,"abstract":"","PeriodicalId":8432,"journal":{"name":"Arkivoc","volume":null,"pages":null},"PeriodicalIF":0.9,"publicationDate":"2024-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139526818","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-01-15DOI: 10.24820/ark.5550190.p012.115
John A. Murphy, Chelsea D Grace, Simon Nicolle
The combination of modern radical generation strategies and the radical C-H functionalisation of heteroaromatics (the Minisci reaction) offers attractive routes to the preparation of complex fused heteroaromatic compounds. In this work, the one-step preparation of a trifunctionalised spiro-azaindane was investigated through a radical cascade route. In an effort to determine the most efficient approach, this cascade was initiated by 4 different radical precursors, in varying yields, adapting recently developed protocols. The best results were achieved using a triphenylpyridinium salt (Katritzky salt) under visible light irradiation
{"title":"Investigations into the radical cascade route to a spiro-azaindane","authors":"John A. Murphy, Chelsea D Grace, Simon Nicolle","doi":"10.24820/ark.5550190.p012.115","DOIUrl":"https://doi.org/10.24820/ark.5550190.p012.115","url":null,"abstract":"The combination of modern radical generation strategies and the radical C-H functionalisation of heteroaromatics (the Minisci reaction) offers attractive routes to the preparation of complex fused heteroaromatic compounds. In this work, the one-step preparation of a trifunctionalised spiro-azaindane was investigated through a radical cascade route. In an effort to determine the most efficient approach, this cascade was initiated by 4 different radical precursors, in varying yields, adapting recently developed protocols. The best results were achieved using a triphenylpyridinium salt (Katritzky salt) under visible light irradiation","PeriodicalId":8432,"journal":{"name":"Arkivoc","volume":null,"pages":null},"PeriodicalIF":0.9,"publicationDate":"2024-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139437527","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-01-15DOI: 10.24820/ark.5550190.p012.093
Andrew D Smith, Matthew T Westwood, Kevin Kasten, Lotte Stockhammer, R. D. Río-Rodríguez, Jose A. Fernández‐Salas, Andreas Eitzinger, Alexandra M. Z. Slawin, Mario Waser, José Alemán, Armin Ofial
The incorporation of the CF 2 motif within organic structures is known to affect the susceptibility of functional groups to oxidation, as well as altering conformation and reactivity. In this manuscript, the incorporation of the CF 2 functional group within an isothiourea catalyst skeleton to give C(3)-F 2 -HBTM is reported. Effective gram-scale routes to both racemic and enantiopure heterocyclic Lewis bases are developed, with preliminary catalytic and kinetic activity evaluated
{"title":"Unveiling the Impact of a CF2 motif in the Isothiourea Catalyst Skeleton: Evaluating C(3)-F2-HBTM and its Catalytic Activity","authors":"Andrew D Smith, Matthew T Westwood, Kevin Kasten, Lotte Stockhammer, R. D. Río-Rodríguez, Jose A. Fernández‐Salas, Andreas Eitzinger, Alexandra M. Z. Slawin, Mario Waser, José Alemán, Armin Ofial","doi":"10.24820/ark.5550190.p012.093","DOIUrl":"https://doi.org/10.24820/ark.5550190.p012.093","url":null,"abstract":"The incorporation of the CF 2 motif within organic structures is known to affect the susceptibility of functional groups to oxidation, as well as altering conformation and reactivity. In this manuscript, the incorporation of the CF 2 functional group within an isothiourea catalyst skeleton to give C(3)-F 2 -HBTM is reported. Effective gram-scale routes to both racemic and enantiopure heterocyclic Lewis bases are developed, with preliminary catalytic and kinetic activity evaluated","PeriodicalId":8432,"journal":{"name":"Arkivoc","volume":null,"pages":null},"PeriodicalIF":0.9,"publicationDate":"2024-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139437137","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-01-09DOI: 10.24820/ark.5550190.p012.028
Mohammad Piltan, Hadis Bahrami
An efficient, one – pot three component synthesis of novel stable phosphorus ylides has been developed from the reaction between triphenylphosphine and dialkyl acetylenedicarboxylates in the presence of 2-nitrocyclohexanone. The resulting phosphorus ylides when heated in toluene afforded dialkyl 2-(2-nitrocyclohex-1-enyl)fumarate derivatives through intramolecular Wittig reaction.
{"title":"Three-component reaction of triphenylphosphine, dialkyl acetylenedicarboxylates, and 2-nitrocyclohexanone","authors":"Mohammad Piltan, Hadis Bahrami","doi":"10.24820/ark.5550190.p012.028","DOIUrl":"https://doi.org/10.24820/ark.5550190.p012.028","url":null,"abstract":"An efficient, one – pot three component synthesis of novel stable phosphorus ylides has been developed from the reaction between triphenylphosphine and dialkyl acetylenedicarboxylates in the presence of 2-nitrocyclohexanone. The resulting phosphorus ylides when heated in toluene afforded dialkyl 2-(2-nitrocyclohex-1-enyl)fumarate derivatives through intramolecular Wittig reaction.","PeriodicalId":8432,"journal":{"name":"Arkivoc","volume":null,"pages":null},"PeriodicalIF":0.9,"publicationDate":"2024-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139380035","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-01-09DOI: 10.24820/ark.5550190.p012.110
Heiko Ihmels, Philip N. Gross, P. M. Pithan
The Rh-catalyzed annulation reaction of 2-(ethynylaryl)ethaneamines was used as key step to synthesize two berberine derivatives with hydroxy and phenyl substituents in 11-and 13-position. These compounds showed absorption and emission properties comparable to the parent alkaloid berberine. The fluorescence of the hydroxy-substituted berberine (p K a = 6.3) is efficiently quenched under acidic conditions, whereas a fluorescence light-up effect was observed with increasing pH values. The interactions of the berberine derivatives with duplex DNA and quadruplex DNA were investigated with absorption, circular dichroism (CD), and linear dichroism (LD) spectroscopy. The 13-phenyl-substituted berberine binds to duplex DNA with a binding constant of K b = 1.2 10 5 M −1 and to quadruplex DNA with K b = 1.9 10 5 M −1 . The CD-and LD-spectroscopic studies showed that the 11-hydroxy-13-phenyl-substituted berberine binds to duplex DNA by intercalation and to quadruplex DNA by terminal π stacking.
以 Rh 催化的 2-(乙炔芳基)乙烷胺环化反应为关键步骤，合成了 11 位和 13 位带有羟基和苯基取代基的两种小檗碱衍生物。这些化合物的吸收和发射特性与母体生物碱小檗碱相当。在酸性条件下，羟基取代的小檗碱（p K a = 6.3）的荧光会被有效淬灭，而随着 pH 值的增加，荧光会出现增强效应。研究人员利用吸收、圆分色（CD）和线性分色（LD）光谱分析了小檗碱衍生物与双链 DNA 和四链 DNA 的相互作用。13 苯基取代的小檗碱与双链 DNA 的结合常数为 K b = 1.2 10 5 M -1 ，与四链 DNA 的结合常数为 K b = 1.9 10 5 M -1 。CD 和 LD 光谱研究表明，11-羟基-13-苯基取代的小檗碱通过插层与双链 DNA 结合，通过末端 π 堆积与四链 DNA 结合。
{"title":"RhIII-catalyzed synthesis and investigation of the DNA-binding properties of 11- and 13-substituted berberine derivatives","authors":"Heiko Ihmels, Philip N. Gross, P. M. Pithan","doi":"10.24820/ark.5550190.p012.110","DOIUrl":"https://doi.org/10.24820/ark.5550190.p012.110","url":null,"abstract":"The Rh-catalyzed annulation reaction of 2-(ethynylaryl)ethaneamines was used as key step to synthesize two berberine derivatives with hydroxy and phenyl substituents in 11-and 13-position. These compounds showed absorption and emission properties comparable to the parent alkaloid berberine. The fluorescence of the hydroxy-substituted berberine (p K a = 6.3) is efficiently quenched under acidic conditions, whereas a fluorescence light-up effect was observed with increasing pH values. The interactions of the berberine derivatives with duplex DNA and quadruplex DNA were investigated with absorption, circular dichroism (CD), and linear dichroism (LD) spectroscopy. The 13-phenyl-substituted berberine binds to duplex DNA with a binding constant of K b = 1.2 10 5 M −1 and to quadruplex DNA with K b = 1.9 10 5 M −1 . The CD-and LD-spectroscopic studies showed that the 11-hydroxy-13-phenyl-substituted berberine binds to duplex DNA by intercalation and to quadruplex DNA by terminal π stacking.","PeriodicalId":8432,"journal":{"name":"Arkivoc","volume":null,"pages":null},"PeriodicalIF":0.9,"publicationDate":"2024-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139379905","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-01-07DOI: 10.24820/ark.5550190.p012.112
Samir Z. Zard
This account is a collection of vignettes describing new reactions discovered in the author ’ s group revolving around the chemistry of oximes. They range from ionic transformations, including reduction to unsubstituted imines and the formation of -electrophiles, to the generation and capture of iminyl radicals, to a general synthesis of alkynes. The mechanistic reasonings and occasional serendipitous observations underlying these discoveries are discussed briefly
{"title":"Chemical Adventures with Oximes","authors":"Samir Z. Zard","doi":"10.24820/ark.5550190.p012.112","DOIUrl":"https://doi.org/10.24820/ark.5550190.p012.112","url":null,"abstract":"This account is a collection of vignettes describing new reactions discovered in the author ’ s group revolving around the chemistry of oximes. They range from ionic transformations, including reduction to unsubstituted imines and the formation of -electrophiles, to the generation and capture of iminyl radicals, to a general synthesis of alkynes. The mechanistic reasonings and occasional serendipitous observations underlying these discoveries are discussed briefly","PeriodicalId":8432,"journal":{"name":"Arkivoc","volume":null,"pages":null},"PeriodicalIF":0.9,"publicationDate":"2024-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139380299","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-01-03DOI: 10.24820/ark.5550190.p012.123
R. Saicic, Milena Veselin Trmcic, Bojan Zoran Vulovic, Matija Sergio Zlatar
Hemiacetals of cyclopropanone can be isolated and stocked, contrary to their highly reactive parent ketone. However, they are not readily converted to cyclopropanone, which limits their use as its synthetic equivalents. 2,2.2-trifluoroethoxy hemiacetals are expected to be better cyclopropanone surrogates, however, they have never been prepared, so far. We show that oxyallyl cations with a heteroatom in the -position can be intercepted with 2,2.2-trifluoroethanol, with formation of cyclopropanone trifluoroethoxy hemiacetals stable enough to be isolated, purified and characterized. These species can serve as synthetic equivalents of cyclopropanone under mild conditions.
{"title":"Preparation of cyclopropanone 2,2,2-trifluoroethoxy hemiacetals via oxyallyl cation","authors":"R. Saicic, Milena Veselin Trmcic, Bojan Zoran Vulovic, Matija Sergio Zlatar","doi":"10.24820/ark.5550190.p012.123","DOIUrl":"https://doi.org/10.24820/ark.5550190.p012.123","url":null,"abstract":"Hemiacetals of cyclopropanone can be isolated and stocked, contrary to their highly reactive parent ketone. However, they are not readily converted to cyclopropanone, which limits their use as its synthetic equivalents. 2,2.2-trifluoroethoxy hemiacetals are expected to be better cyclopropanone surrogates, however, they have never been prepared, so far. We show that oxyallyl cations with a heteroatom in the -position can be intercepted with 2,2.2-trifluoroethanol, with formation of cyclopropanone trifluoroethoxy hemiacetals stable enough to be isolated, purified and characterized. These species can serve as synthetic equivalents of cyclopropanone under mild conditions.","PeriodicalId":8432,"journal":{"name":"Arkivoc","volume":null,"pages":null},"PeriodicalIF":0.9,"publicationDate":"2024-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139118258","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-01-03DOI: 10.24820/ark.5550190.p012.123
R. Saicic, Milena Veselin Trmcic, Bojan Zoran Vulovic, Matija Sergio Zlatar
Hemiacetals of cyclopropanone can be isolated and stocked, contrary to their highly reactive parent ketone. However, they are not readily converted to cyclopropanone, which limits their use as its synthetic equivalents. 2,2.2-trifluoroethoxy hemiacetals are expected to be better cyclopropanone surrogates, however, they have never been prepared, so far. We show that oxyallyl cations with a heteroatom in the -position can be intercepted with 2,2.2-trifluoroethanol, with formation of cyclopropanone trifluoroethoxy hemiacetals stable enough to be isolated, purified and characterized. These species can serve as synthetic equivalents of cyclopropanone under mild conditions.
{"title":"Preparation of cyclopropanone 2,2,2-trifluoroethoxy hemiacetals via oxyallyl cation","authors":"R. Saicic, Milena Veselin Trmcic, Bojan Zoran Vulovic, Matija Sergio Zlatar","doi":"10.24820/ark.5550190.p012.123","DOIUrl":"https://doi.org/10.24820/ark.5550190.p012.123","url":null,"abstract":"Hemiacetals of cyclopropanone can be isolated and stocked, contrary to their highly reactive parent ketone. However, they are not readily converted to cyclopropanone, which limits their use as its synthetic equivalents. 2,2.2-trifluoroethoxy hemiacetals are expected to be better cyclopropanone surrogates, however, they have never been prepared, so far. We show that oxyallyl cations with a heteroatom in the -position can be intercepted with 2,2.2-trifluoroethanol, with formation of cyclopropanone trifluoroethoxy hemiacetals stable enough to be isolated, purified and characterized. These species can serve as synthetic equivalents of cyclopropanone under mild conditions.","PeriodicalId":8432,"journal":{"name":"Arkivoc","volume":null,"pages":null},"PeriodicalIF":0.9,"publicationDate":"2024-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139122116","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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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