Review
Chemistry, Physical
Tong-De Tan, Ze-Shu Wang, Peng-Cheng Qian, Long-Wu Ye
Summary: Ynamides, as electron-rich heteroatom-substituted alkynes, have proven to be versatile reagents for organic synthesis and have received extensive attention. Radical reactions of ynamides, categorized by radical attack at the alpha-position and beta-position, are reviewed in this article to highlight reaction selectivity, scope, mechanism, and applicability. The aim is to provide a comprehensive summarization of these advances to guide the further development of ynamide chemistry.
Article
Chemistry, Applied
Atsushi Umehara, Soma Shimizu, Makoto Sasaki
Summary: This report presents a general method for the direct N-acylation of N-heterocycles using the DMAPO/Boc(2)O system. This one-pot method allows for the synthesis of bulky N-acyl heterocycles from less nucleophilic N-heterocycles and sterically hindered carboxylic acids. The protocol has also been successfully applied to the one-pot N-acylation of 7-azaindoles.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Robert D. Riley, Blake S. N. Huchenski, Karlee L. Bamford, Alexander W. H. Speed
Summary: This study demonstrates that diazaphospholene hydrides can be regenerated by the combination of phenylsilane and alkali metal salts, enabling catalytic radical reactions of aryl iodides. The method is not only applicable to aryl iodides, but can also be extended to aryl bromides, which benefit from visible light irradiation. Additionally, intermolecular radical hydroarylation reactions with arenes, thiophenes, and a pyridine have been successfully achieved.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Atsushi Umehara, Soma Shimizu, Makoto Sasaki
Summary: This report presents a practical and operationally simple method for the direct N-acylation of less nucleophilic heterocycles and amides with carboxylic acids. The method utilizes the DMAPO/Boc(2)O system and does not require pre-activation of substrates. It demonstrates high yield, excellent functional group tolerance, and broad substrate scope, making it suitable for both academic and industrial laboratories.
Article
Chemistry, Multidisciplinary
Johannes Grosskopf, Alexandra A. Heidecker, Thorsten Bach
Summary: Racemic 3-substituted oxindoles can be converted into enantiomerically pure or enriched material through photochemical deracemization process. Light energy compensates for the loss of entropy and enables predictable editing of the stereogenic center. The obtained oxindoles are valuable intermediates for further transformations with complete retention at the stereogenic center.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Jacob C. Hood, Yannick Tshikaya, Aaren R. Manz, Marcus C. LaPorte, Douglas A. Klumpp
Summary: In this study, a series of conjugate addition reactions were successfully performed using vinyl-substituted N-heterocycles in acid-catalyzed conversions, resulting in the formation of pyridyl and related heterocyclic products. The nucleophiles used in these reactions include 1,3-dicarbonyl compounds, cyano esters, cyano sulfone, and malonylnitrile, while the Michael accepting groups include vinyl-substituted pyridines, quinoline, and pyrazine. Double conjugate addition reactions were also achieved using 2,6-divinylpyridine and related systems.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Xiang Chen, Jun Jiang, Xiao-Jun Huang, Wei-Min He
Summary: An electrochemical oxidative strategy for the synthesis of benzoxazines without transition-metal catalysts and external oxidants is described. Olefinic amides can be transferred to difluoromethylated benzoxazines with up to 87% yield via oxydifluoromethylation using CF2HSO2Na as the reagent in an undivided cell.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Polymer Science
Michael R. Martinez, Ziye Zhuang, Megan Treichel, Julia Cuthbert, Mingkang Sun, Joanna Pietrasik, Krzysztof Matyjaszewski
Summary: In this study, photoinduced atom transfer radical polymerization (photoATRP) and atom transfer radical coupling (ATRC) were used to prepare a thermally labile polymer network. The results showed that the polymer network can undergo inversion at high temperatures.
Article
Chemistry, Organic
Jacob C. Hood, Maksim V. Anokhin, Douglas A. Klumpp
Summary: N-Heterocyclic alcohols have been proven to be excellent substrates for superacid-promoted Friedel-Crafts reactions. The ionization of N-heterocyclic alcohols produces reactive, dicationic intermediates, leading to good to excellent yields of arylation products.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Zican Shen, Maria A. Vargas-Rivera, Elizabeth L. Rigby, Shuming Chen, Jonathan A. Ellman
Summary: A photocatalyzed epimerization of morpholines and piperazines has been reported using reversible hydrogen atom transfer (HAT), providing an efficient strategy for editing the stereochemical configurations of these saturated nitrogen heterocycles prevalent in drugs.
Article
Chemistry, Applied
Ban Wang, Gavin E. Mccabe, Mitchell J. Parrish, Jujhar Singh, Matthias Zeller, Yongming Deng
Summary: A photoinduced selective hydroamination reaction of ynamides with nitrogen heteroaromatic nucleophiles has been developed using an organocatalytic photoredox system. This method allows for the direct construction of a diverse range of (Z)-alpha-azole enamides from ynamides and pyrazoles, triazoles, benzotriazoles, indazoles, and tetrazoles, providing a photocatalytic synthetic route to heterocyclic motifs commonly found in medicinal agents.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Nicolaj Inunnguaq Jessen, Maksimilian Bura, Giulio Bertuzzi, Karl Anker Jorgensen
Summary: An efficient and stereoselective synthesis of chiral cycl[3.2.2]azines has been achieved through the rational design and utilization of novel (E)-3-benzylidene-3H-pyrrolizines in iminium-ion catalysis. The method allows for incorporation of diverse enals and the obtained products can undergo selective transformations while retaining stereochemical information established in the [8+2] cycloaddition.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Kai Oberdorf, Anna Hanft, Jacqueline Ramler, Ivo Krummenacher, F. Matthias Bickelhaupt, Jordi Poater, Crispin Lichtenberg
Summary: The controlled release of aminyl radicals from bismuth amide species at ambient temperature enables selective N-N coupling reactions to yield hydrazines. Analyzes using various spectroscopy techniques and calculations reveal low homolytic bond-dissociation energies, suggesting radical coupling in the coordination sphere of bismuth, and demonstrate the effectiveness of electronic and steric parameters in controlling these reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Medicinal
Junhui Lu, Huimin Zhang, Jinhui Yu, Dezun Shan, Ji Qi, Jiawen Chen, Hongwei Song, Minghui Yang
Summary: The study developed a machine learning approach to predict the temperature-dependent site-specific rate constants of hydrogen abstraction reactions, demonstrating robustness in accurately predicting the site-specific and overall rate constants.
JOURNAL OF CHEMICAL INFORMATION AND MODELING
(2021)
Article
Chemistry, Multidisciplinary
Shahilan Ratnam, Shreya Unone, Daniel Janssen-Mueller
Summary: It is found that alkyl-substituted dihydroquinolines derived from 2,2'-biquinoline can serve as efficient radical precursors, forming primary, secondary, and tertiary alkyl radicals. Copper catalysis allows the hydroalkylation of benzalmalononitriles and N-Boc protected diazenes under mild conditions, with yields up to 85%. The reactivity of the dihydroquinolines towards denitrative alkylation of nitroolefins, such as β-nitrostyrene, has been discovered. Notably, the released biquinoline can be recycled, greatly improving the atom-economy of these alkyl radical precursors compared to previous N-heterocyclic electroauxiliaries.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Plant Sciences
Caroline Bosch, Ben Bradshaw, Josep Bonjoch
JOURNAL OF NATURAL PRODUCTS
(2019)
Article
Chemistry, Organic
Sergi Jansana, Faiza Diaba, Josep Bonjoch
Article
Chemistry, Multidisciplinary
Sergi Jansana, Guilhem Coussanes, Jordi Puig, Faiza Diaba, Josep Bonjoch
HELVETICA CHIMICA ACTA
(2019)
Article
Chemistry, Organic
Mar Saladrigas, Josep Bonjoch, Ben Bradshaw
Review
Chemistry, Organic
Josep Bonjoch, Faiza Diaba
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Chemistry, Organic
Mar Saladrigas, Jordi Puig, Josep Bonjoch, Ben Bradshaw
Article
Chemistry, Organic
Claudia Marques, Faiza Diaba, Enrique Gomez-Bengoa, Josep Bonjoch
Summary: A synthetic approach to functionalized ABC-tricyclic framework of calyciphilline A-type alkaloids is reported, which involves radical cyclization and stereocontrolled aldol cyclization. The resulting compound serves as a building block for this class of alkaloids, and the synthesis of azatricyclic compound I constitutes a formal synthesis of himalensine A.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Laura G. Rodriguez, Ana Delgado, Carlos J. Ciudad, Veronique Noe, Josep Bonjoch, Ben Bradshaw
Summary: A two-step reaction was developed to synthesize a ring system found in natural products. The reaction was explored with eight substituted nitrobenzenes, achieving yields of up to 87%. One of the benzazocine compounds, 4h, exhibited high cytotoxicity and was active against eight cancer cell lines.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Faiza Diaba, Alexandra G. Sandor, Maria del Carmen Moran
Summary: Natural and synthetic beta-lactam derivatives are a class of compounds with diverse biological activity, including antibiotics, antitubercular, anticancer, and antidiabetic activities. This study evaluated the hemolytic and cytotoxic properties of six new 3,3-dichloro-beta-lactams. The results showed that these compounds are non-hemolytic and exhibited interesting cytotoxic activity against squamous cell carcinoma, with the most cytotoxic compound being 2b.
Article
Chemistry, Organic
Gisela Trenchs, Faiza Diaba
Summary: The first blue light-mediated synthesis of gamma- and delta-lactams from trichloroacetamides is reported. Unlike previous works, these reactions can be achieved under an air atmosphere with non-anhydrous solvents and even in water. Moreover, it has been demonstrated that the solvent can act as the hydrogen donor in the radical process, providing new insights into these radical transformations and the reaction mechanisms involved.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Organic
Claudia Marques, Faiza Diaba, Jaume Roca, Josep Bonjoch
Summary: The 5-endo-trig radical cyclization of N-benzyl-N-[(2-substituted)cycloalkenyl] trichloroacetamides using Bu3SnH and AIBN provides access to 3a-methyl- and 3a-methoxycarbonyl enelactams. Diastereoselective enolate alkylation of these enelactams leads to the synthesis of a set of 3-substituted derivatives, which can be further reduced to generate polyfunctionalized cis-octahydroindoles containing three consecutive stereocenters at C-3, C-3a, and C-7a. These building blocks can also be synthesized through an initial reductive radical cyclization using (carbo-substituted)dichloroacetamides.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Fuying Zhu, Yamei Lin
Summary: In this study, a low-metal iron-supported catalyst (Fe20/NC-Mg) was reported for the efficient synthesis of quinoxaline compounds, using water as a solvent and without additional bases. The synergistic effect of FeNx site and Mg (OH)2 nanorods in the catalyst played a key role in achieving high yields (82-91%) in 16 examples. The gram-level synthesis and reusability of the catalysts after four cycles demonstrated its industrial application potential.
Article
Chemistry, Organic
Mikhail Kozlov, Alexey Tyurin, Andrey Dmitrenok, Vyacheslav Rusak, Aleksander Fedorov, Igor Zavarzin, Yulia Volkova
Summary: This study presents a novel and practical synthesis method for phosphorus-substituted 1,3,4-thiadiazolines using phosphorylthioformic acid hydrazides and ketones. The protocol demonstrates operational simplicity, availability of reagents, and tolerance towards different functional groups.
Article
Chemistry, Organic
Jisna Jose, Thomas Mathew
Summary: 2-Cyclopentenone and its derivatives are highly esteemed synthetic intermediates with exceptional utility in organic synthesis. They are favored structural motifs in numerous pharmaceutical drugs and natural products, highlighting their significance. The review discusses the various methods used to synthesize cyclopentenones from 2016 to 2023.
