Beilstein Journal of Organic Chemistry最新文献_第10页

Hydrogen-bond activation enables aziridination of unactivated olefins with simple iminoiodinanes 氢键活化使未活化的烯烃与简单的亚氨基碘烷发生氮丙啶化反应

IF 2.7 4区化学

Beilstein Journal of Organic Chemistry Pub Date : 2024-09-11 DOI: 10.3762/bjoc.20.197

Phong Thai, Lauv Patel, Diyasha Manna, David C. Powers

{"title":"Hydrogen-bond activation enables aziridination of unactivated olefins with simple iminoiodinanes","authors":"Phong Thai, Lauv Patel, Diyasha Manna, David C. Powers","doi":"10.3762/bjoc.20.197","DOIUrl":"https://doi.org/10.3762/bjoc.20.197","url":null,"abstract":"Abstract\u0000Iminoiodinanes comprise a class of hypervalent iodine reagents that is often encountered in nitrogen-group transfer (NGT) catalysis. In general, transition metal catalysts are required to effect efficient NGT to unactivated olefins because iminoiodinanes are insufficiently electrophilic to engage in direct aziridination chemistry. Here, we demonstrate that 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) activates N-arylsulfonamide-derived iminoiodinanes for the metal-free aziridination of unactivated olefins. 1H NMR and cyclic voltammetry (CV) studies indicate that hydrogen-bonding between HFIP and the iminoiodinane generates an oxidant capable of direct NGT to unactivated olefins. Stereochemical scrambling during aziridination of 1,2-disubstituted olefins is observed and interpreted as evidence that aziridination proceeds via a carbocation intermediate that subsequently cyclizes. These results demonstrate a simple method for activating iminoiodinane reagents, provide analysis of the extent of activation achieved by H-bonding, and indicate the potential for chemical non-innocence of fluorinated alcohol solvents in NGT catalysis.\u0000<img src='https://www.beilstein-journals.org/bjoc/content/figures/1860-5397-20-197-graphical-abstract.png?max-width=550' border='0'/>\u0000Beilstein J. Org. Chem. 2024, 20, 2305–2312. doi:10.3762/bjoc.20.197","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"14 1","pages":""},"PeriodicalIF":2.7,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142184998","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}

引用次数: 0

Catalysing (organo-)catalysis: Trends in the application of machine learning to enantioselective organocatalysis 催化（有机）催化：机器学习在对映选择性有机催化中的应用趋势

IF 2.7 4区化学

Beilstein Journal of Organic Chemistry Pub Date : 2024-09-10 DOI: 10.3762/bjoc.20.196

Stefan P. Schmid, Leon Schlosser, Frank Glorius, Kjell Jorner

{"title":"Catalysing (organo-)catalysis: Trends in the application of machine learning to enantioselective organocatalysis","authors":"Stefan P. Schmid, Leon Schlosser, Frank Glorius, Kjell Jorner","doi":"10.3762/bjoc.20.196","DOIUrl":"https://doi.org/10.3762/bjoc.20.196","url":null,"abstract":"Abstract\u0000Organocatalysis has established itself as a third pillar of homogeneous catalysis, besides transition metal catalysis and biocatalysis, as its use for enantioselective reactions has gathered significant interest over the last decades. Concurrent to this development, machine learning (ML) has been increasingly applied in the chemical domain to efficiently uncover hidden patterns in data and accelerate scientific discovery. While the uptake of ML in organocatalysis has been comparably slow, the last two decades have showed an increased interest from the community. This review gives an overview of the work in the field of ML in organocatalysis. The review starts by giving a short primer on ML for experimental chemists, before discussing its application for predicting the selectivity of organocatalytic transformations. Subsequently, we review ML employed for privileged catalysts, before focusing on its application for catalyst and reaction design. Concluding, we give our view on current challenges and future directions for this field, drawing inspiration from the application of ML to other scientific domains.\u0000<img src='https://www.beilstein-journals.org/bjoc/content/figures/1860-5397-20-196-graphical-abstract.png?max-width=550' border='0'/>\u0000Beilstein J. Org. Chem. 2024, 20, 2280–2304. doi:10.3762/bjoc.20.196","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"53 1","pages":""},"PeriodicalIF":2.7,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142184999","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}

引用次数: 0

Deuterated reagents in multicomponent reactions to afford deuterium-labeled products 在多组分反应中使用氘化试剂，生成氘标记产品

IF 2.7 4区化学

Beilstein Journal of Organic Chemistry Pub Date : 2024-09-06 DOI: 10.3762/bjoc.20.195

Kevin Schofield, Shayna Maddern, Yueteng Zhang, Grace E. Mastin, Rachel Knight, Wei Wang, James Galligan, Christopher Hulme

{"title":"Deuterated reagents in multicomponent reactions to afford deuterium-labeled products","authors":"Kevin Schofield, Shayna Maddern, Yueteng Zhang, Grace E. Mastin, Rachel Knight, Wei Wang, James Galligan, Christopher Hulme","doi":"10.3762/bjoc.20.195","DOIUrl":"https://doi.org/10.3762/bjoc.20.195","url":null,"abstract":"Abstract\u0000The utility of bio-isosteres is broad in drug discovery and methodology herein enables the preparation of deuterium-labeled products is the most fundamental of known bio-isosteric replacements. As such we report the use of both [D1]-aldehydes and [D2]-isonitriles across 8 multicomponent reactions (MCRs) to give diverse arrays of deuterated products. A highlight is the synthesis of several FDA-approved calcium channel blockers, selectively deuterated at a t1/2 limiting metabolic soft-spot via use of [D1]-aldehydes. Surrogate pharmacokinetic analyses of microsomal stability confirm prolongation of t1/2 of the new deuterated analogs. We also report the first preparation of [D2]-isonitriles from [D3]-formamides via a modified Leuckart–Wallach reaction and their use in an MCR to afford products with [D2]-benzylic positions and likely significantly enhanced metabolic stability, a key parameter for property-based design efforts.\u0000<img src='https://www.beilstein-journals.org/bjoc/content/figures/1860-5397-20-195-graphical-abstract.png?max-width=550' border='0'/>\u0000Beilstein J. Org. Chem. 2024, 20, 2270–2279. doi:10.3762/bjoc.20.195","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"6 1","pages":""},"PeriodicalIF":2.7,"publicationDate":"2024-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142224059","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}

引用次数: 0

gem-Difluorination of carbon–carbon triple bonds using Brønsted acid/Bu4NBF4 or electrogenerated acid gem-使用布氏酸/Bu4NBF4 或电生酸对碳-碳三键进行二氟化反应

IF 2.7 4区化学

Beilstein Journal of Organic Chemistry Pub Date : 2024-09-06 DOI: 10.3762/bjoc.20.194

Mizuki Yamaguchi, Hiroki Shimao, Kengo Hamasaki, Keiji Nishiwaki, Shigenori Kashimura, Kouichi Matsumoto

引用次数: 0

Synthesis and reactivity of the di(9-anthryl)methyl radical 二（9-蒽基）甲基自由基的合成和反应性

IF 2.7 4区化学

Beilstein Journal of Organic Chemistry Pub Date : 2024-09-05 DOI: 10.3762/bjoc.20.193

Tomohiko Nishiuchi, Kazuma Takahashi, Yuta Makihara, Takashi Kubo

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Metal-free double azide addition to strained alkynes of an octadehydrodibenzo[12]annulene derivative with electron-withdrawing substituents 八代氢二苯并[12]萘衍生物与具有电子撤回取代基的受约束炔的无金属双叠氮加成反应

IF 2.7 4区化学

Beilstein Journal of Organic Chemistry Pub Date : 2024-09-04 DOI: 10.3762/bjoc.20.191

Naoki Takeda, Shuichi Akasaka, Susumu Kawauchi, Tsuyoshi Michinobu

引用次数: 0

Cell-free protein synthesis with technical additives – expanding the parameter space of in vitro gene expression 使用技术添加剂的无细胞蛋白质合成--拓展体外基因表达的参数空间

IF 2.7 4区化学

Beilstein Journal of Organic Chemistry Pub Date : 2024-09-04 DOI: 10.3762/bjoc.20.192

Tabea Bartsch, Stephan Lütz, Katrin Rosenthal

{"title":"Cell-free protein synthesis with technical additives – expanding the parameter space of in vitro gene expression","authors":"Tabea Bartsch, Stephan Lütz, Katrin Rosenthal","doi":"10.3762/bjoc.20.192","DOIUrl":"https://doi.org/10.3762/bjoc.20.192","url":null,"abstract":"Abstract\u0000Biocatalysis has established itself as a successful tool in organic synthesis. A particularly fast technique for screening enzymes is the in vitro expression or cell-free protein synthesis (CFPS). The system is based on the transcription and translation machinery of an extract-donating organism to which substrates such as nucleotides and amino acids, as well as energy molecules, salts, buffer, etc., are added. After successful protein synthesis, further substrates can be added for an enzyme activity assay. Although mimicking of cell-like conditions is an approach for optimization, the physical and chemical properties of CFPS are not well described yet. To date, standard conditions have mainly been used for CFPS, with little systematic testing of whether conditions closer to intracellular conditions in terms of viscosity, macromolecules, inorganic ions, osmolarity, or water content are advantageous. Also, very few non-physiological conditions have been tested to date that would expand the parameter space in which CFPS can be performed. In this study, the properties of an Escherichia coli extract-based CFPS system are evaluated, and the parameter space is extended to high viscosities, concentrations of inorganic ion and osmolarity using ten different technical additives including organic solvents, polymers, and salts. It is shown that the synthesis of two model proteins, namely superfolder GFP (sfGFP) and the enzyme truncated human cyclic GMP-AMP synthase fused to sfGFP (thscGAS-sfGFP), is very robust against most of the tested additives.\u0000<img src='https://www.beilstein-journals.org/bjoc/content/figures/1860-5397-20-192-graphical-abstract.png?max-width=550' border='0'/>\u0000Beilstein J. Org. Chem. 2024, 20, 2242–2253. doi:10.3762/bjoc.20.192","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"29 1","pages":""},"PeriodicalIF":2.7,"publicationDate":"2024-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142185002","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}

引用次数: 0

Selective hydrolysis of α-oxo ketene N,S-acetals in water: switchable aqueous synthesis of β-keto thioesters and β-keto amides α-氧代酮 N,S-乙醛在水中的选择性水解：β-酮硫代酯和β-酮酰胺的可切换水性合成

IF 2.7 4区化学

Beilstein Journal of Organic Chemistry Pub Date : 2024-09-03 DOI: 10.3762/bjoc.20.190

Haifeng Yu, Wanting Zhang, Xuejing Cui, Zida Liu, Xifu Zhang, Xiaobo Zhao

{"title":"Selective hydrolysis of α-oxo ketene N,S-acetals in water: switchable aqueous synthesis of β-keto thioesters and β-keto amides","authors":"Haifeng Yu, Wanting Zhang, Xuejing Cui, Zida Liu, Xifu Zhang, Xiaobo Zhao","doi":"10.3762/bjoc.20.190","DOIUrl":"https://doi.org/10.3762/bjoc.20.190","url":null,"abstract":"Abstract\u0000An eco-friendly selective hydrolysis of chain α-oxo ketene N,S-acetals in water for the switchable synthesis of β-keto thioesters and β-keto amides is reported. In refluxing water, the hydrolysis reactions of α-oxo ketene N,S-acetals in the presence of 1.0 equiv of dodecylbenzenesulfonic acid effectively afforded β-keto thioesters in excellent yield, while β-keto amides were successfully obtained in excellent yield when the hydrolysis reactions were carried out in the presence of 3.0 equiv of NaOH. The green approach to β-keto thioesters and β-keto amides avoids the use of harmful organic solvents, thiols and thiolacetates as well as amines, which could result in serious environmental and safety issues.\u0000<img src='https://www.beilstein-journals.org/bjoc/content/figures/1860-5397-20-190-graphical-abstract.png?max-width=550' border='0'/>\u0000Beilstein J. Org. Chem. 2024, 20, 2225–2233. doi:10.3762/bjoc.20.190","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"4 1","pages":""},"PeriodicalIF":2.7,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142185003","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}

引用次数: 0

Heterocycle-guided synthesis of m-hetarylanilines via three-component benzannulation 通过三组份苯并吡喃法异氰酸酯引导合成间位苯乙烯类化合物

IF 2.7 4区化学

Beilstein Journal of Organic Chemistry Pub Date : 2024-09-02 DOI: 10.3762/bjoc.20.188

Andrey R. Galeev, Maksim V. Dmitriev, Alexander S. Novikov, Andrey N. Maslivets

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Electrochemical allylations in a deep eutectic solvent 深共晶溶剂中的电化学烯丙基化反应

IF 2.7 4区化学

Beilstein Journal of Organic Chemistry Pub Date : 2024-09-02 DOI: 10.3762/bjoc.20.189

Sophia Taylor, Scott T. Handy

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