Article
Chemistry, Multidisciplinary
Alexander Purtsas, Marco Rosenkranz, Evgenia Dmitrieva, Olga Kataeva, Hans-Joachim Knoelker
Summary: In this paper, the oxygenation and amination reactions of tertiary arylamines are described. The key steps of these coupling reactions involve iron-catalyzed oxidative C-O or C-N bond formation, which typically provide the desired products in high yields and with excellent regioselectivity. These transformations are carried out using hexadecafluorophthalocyanine-iron(II) (FePcF16) as catalyst, with the presence of an acid or base additive, and only require ambient air as the oxidant.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Pooja Y. Vemuri, Frederic W. Patureau
Summary: In this study, an unprecedented, simple and hetero-selective cross-dehydrogenative N-N coupling of amides and benzotriazoles using a hypervalent iodine species as the terminal oxidant was reported. The scope and mechanistic investigations of this reaction were discussed.
Review
Chemistry, Organic
C. M. A. Afsina, Thaipparambil Aneeja, Mohan Neetha, Gopinathan Anilkumar
Summary: Copper-catalyzed organic reactions have attracted widespread attention due to the abundance and affordability of copper, as well as its low toxicity, eco-friendliness, sustainable nature, and versatility as a catalyst. These reactions are primarily used for the synthesis of biologically important nitrogen heterocycles, amines, amides, imines, and alkynes.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Marc Strohmann, Andreas J. Vorholt, Walter Leitner
Summary: This study presents a method for transforming olefins into branched amines by combining hydroformylation/aldol condensation tandem reaction with reductive amination. The method utilizes a combined multiphase system that can be recycled 9 times. The study demonstrates the feasibility of the method and its potential applications in the production of surfactants.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Xiao-Wen Wang, Rui-Xue Li, Yang Deng, Ming-Qiu-Hao Fu, Ya-Nan Zhao, Zhi Guan, Yan-Hong He
Summary: This article proposes a new method for the direct hydroxylarylation of unactivated benzylic carbons (sp3/sp2/sp) without the need for pre-functionalized benzylic alcohols, aromatic aldehydes, or ketones. It features direct functionalization of unactivated benzylic C(sp3)-H bonds and benzylic sp2/sp-carbons, mild conditions (open air, room temperature), an environmentally friendly procedure (without any external catalyst/mediator/additive), and direct access to sterically hindered alcohols from inexpensive and readily available alkyl/alkenyl/alkynylbenzenes. Mechanistic studies strongly support the proposed radical-radical cross-coupling between transient ketyl radicals and persistent radical anions. Gram-scale synthesis and diversification of drug derivatives demonstrate the practical potential of this protocol.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Jinghui Zhang, Meng Zhang, Yumeng Shi
Summary: This report presents a metal-free convergent paired electrolysis strategy for the synthesis of alpha-benzyl amine from imines and methylarenes, utilizing both anodic oxidation and cathodic reduction. The key to the success of this electrolysis is the simultaneous matching of desirable half reactions, leading to the desired product.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Multidisciplinary Sciences
Shuaishuai Wang, Tingrui Li, Chengyihan Gu, Jie Han, Chuan-Gang Zhao, Chengjian Zhu, Hairen Tan, Jin Xie
Summary: This article reports on an iron-catalyzed reaction for efficient construction of aromatic tertiary amines, which is important in drug discovery and organic chemistry. The reaction employs a radical tandem C-N coupling strategy and can synthesize nonsymmetric aromatic tertiary amines under mild conditions.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Applied
Yingbo Shao, Zhiyuan Ren, Chenfengtao Zheng, Xiao-Song Xue
Summary: In this study, we computationally investigated the mechanism and origin of the reactivity difference between N-triflylimino-lambda(3)-iodane and N-triflylimino-lambda(3)-bromane in C-H amination and alkene aziridination. Our calculations revealed that the formation of a free nitrene intermediate is the preferred mechanism for C-H amination, while a concerted reaction mechanism is involved in the alkene aziridination. The higher reactivity of N-triflylimino-lambda(3)-bromane compared to N-triflylimino-lambda(3)-iodane can mainly be attributed to the better nucleofugality of the bromanyl moiety, which can be characterized by the strength of the I-N and Br-N bonds. The impact of solvent polarity on the reactivity of N-triflylimino-lambda(3)-bromane as a nitrene precursor is also discussed.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Subrata K. Ghosh, Mengnan Hu, Robert J. Comito
Summary: The method describes a mild and selective protocol for preparing primary and secondary aliphatic amines in a single pot based on intermolecular sp(3) C-H imination. It constitutes a selective method for complex amine synthesis and a new mechanistic platform for C-H amination. This work demonstrates useful site selectivity within substrates bearing multiple sp(3) C-H bonds.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Medicinal
Hirotaka Sasa, Koyo Mori, Kotaro Kikushima, Yasuyuki Kita, Toshifumi Dohi
Summary: Benzolactams have unique biological activity and high utility in organic synthesis and the preparation of oxindole alkaloids and antibacterial agents. The multistep process for their preparation can be bypassed by using C-H amination reactions to directly convert aromatic C(sp(2))-H bonds to C(sp(2))-N bonds. This study describes an effective intramolecular oxidative C-H amination reaction based on mu-oxo hypervalent iodine catalysis for the synthesis of benzolactams.
CHEMICAL & PHARMACEUTICAL BULLETIN
(2022)
Article
Chemistry, Multidisciplinary
Nikki J. Bakas, Jeffrey D. Sears, William W. Brennessel, Michael L. Neidig
Summary: This study provides critical insights into the role of TMEDA as an additive in iron-catalyzed cross-coupling reactions. By using spectroscopic and crystallographic techniques, TMEDA-iron(II)-aryl intermediates are identified in the reaction cycle and it is found that their recombination with radicals leads to highly selective product formation. This research highlights the significance of TMEDA in modulating the selectivity and catalytic performance of organoiron species in cross-coupling reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Physical
Marta Papis, Francesca Foschi, Sara Colombo, Egle Maria Beccalli, Camilla Loro, Gianluigi Broggini
Summary: The combination of copper catalysts and hypervalent iodine reagents is a versatile tool in organic synthesis for the functionalization of unactivated substrates, allowing access to various classes of compounds.
Review
Chemistry, Organic
Chunngai Hui, Andrey P. Antonchick
Summary: This study introduces a new reactive electrophilic aminating reagent, iodonitrene, which can transfer NH-group directly to nucleophilic atoms and has led to the development of new reactions. The application of iodonitrene has promising prospects, although there are current limitations.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Sara Lopez-Resano, Sara Martinez de Salinas, Felipe A. Garces-Pineda, Andrea Moneo-Corcuera, Jose Ramon Galan-Mascaros, Feliu Maseras, Monica H. Perez-Temprano
Summary: The potential access to Co-IV species to promote transformations challenging at Co-III in Cp*Co-catalyzed C-H functionalization reactions remains underexploited. We reveal the participation of Cp*Co-IV species in a Cp*Co-mediated C-S bond-reductive elimination through a combined experimental and computational strategy. These studies support the intermediacy of high-valent Cp*Co species in C-H functionalization reactions, particularly when involving nucleophilic coupling partners under oxidative conditions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Cristian Cavedon, Sebastian Gisbertz, Susanne Reischauer, Sarah Vogl, Eric Sperlich, John H. Burke, Rachel F. Wallick, Stefanie Schrottke, Wei-Hsin Hsu, Lucia Anghileri, Yannik Pfeifer, Noah Richter, Christian Teutloff, Henrike Mueller-Werkmeister, Dario Cambie, Peter H. Seeberger, Josh Vura-Weis, Renske M. van der Veen, Arne Thomas, Bartholomaus Pieber
Summary: We demonstrate visible-light-mediated carbon-heteroatom cross-coupling reactions using a photoactive Ni(II) precatalyst. The activation of this precatalyst involves an initial intraligand charge transfer event triggered by visible light irradiation. Additionally, a porous, recyclable organic polymer for heterogeneous nickel catalysis of cross-coupling reactions is obtained through ligand polymerization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Ali Nasrallah, Vincent Boquet, Alexandra Hecker, Pascal Retailleau, Benjamin Darses, Philippe Dauban
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2019)
Review
Biochemistry & Molecular Biology
Amanda G. Jarvis
CURRENT OPINION IN CHEMICAL BIOLOGY
(2020)
Article
Chemistry, Organic
Benjamin Darses, Pascale Maldivi, Christian Philouze, Philippe Dauban, Jean-Francois Poisson
Summary: Bicyclic compounds with a quaternary stereogenic center were synthesized using asymmetric intramolecular Buchner reaction with high yields and enantioselectivity. X-ray crystallography revealed unexpected behavior in the crystal structure, including equilibrating valence isomers in the solid state, and DFT calculations supported these findings.
Article
Chemistry, Organic
Sebastian J. Castro, Jose M. Padron, Benjamin Darses, Viviana E. Nicotra, Philippe Dauban
Summary: A set of new guaianolide derivatives were obtained through catalytic nitrene transfer reactions, leading to intermolecular nitrene C(sp(3))-H insertions and alkene aziridination. The results showed enhanced biological activity following amination at the C-2 position of Ludartin, highlighting the potential of late-stage C-H amination for improving the bioactivity of natural products.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Biochemistry & Molecular Biology
Richard C. Brewster, Eva Klemencic, Amanda G. Jarvis
Summary: Palladium-catalysed reactions are widely used in organic chemistry, including in biological settings for protein modification and drug decaging. Overcoming challenges such as catalyst poisons and milder reaction conditions in biological media is crucial for successful application of palladium catalysis in biological systems.
JOURNAL OF INORGANIC BIOCHEMISTRY
(2021)
Article
Chemistry, Physical
Megan Doble, Lorenz Obrecht, Henk-Jan Joosten, Misun Lee, Henriette J. Rozeboom, Emma Branigan, James H. Naismith, Dick B. Janssen, Amanda G. Jarvis, Paul C. J. Kamer
Summary: Protein engineering has been used to improve the thermostability of an artificial metalloenzyme, resulting in enhanced activity in high-temperature reactions. The modified metalloenzymes showed a significant increase in turnover number during the hydroformylation of 1-octene, while maintaining a high selectivity for linear aldehyde above 80%.
Article
Chemistry, Multidisciplinary
Yanis Lazib, Pascal Retailleau, Tanguy Saget, Benjamin Darses, Philippe Dauban
Summary: The study presents a streamlined strategy for the asymmetric synthesis of enantiopure pyrrolidines, involving two sequential C-H functionalizations of simple hydrocarbons. The process includes a regio- and stereoselective catalytic nitrene C-H insertion followed by a diastereoselective cyclization to form the pyrrolidines.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Editorial Material
Chemistry, Physical
Amanda G. Jarvis
Summary: Many synthetic chemists aspire to control the subtle differences in reaction mechanisms and outcomes. Protein evolution has enabled the control of selectivity for hydroamination reactions catalysed by gold-based artificial metalloenzymes by favoring dual-gold catalysis over monomeric catalysis.
Article
Multidisciplinary Sciences
Richard C. Brewster, Irati Colmenero Labeaga, Catriona E. Soden, Amanda G. Jarvis
Summary: The study demonstrates the synthesis of cyclic peptides through solid-phase synthesis of peptides containing metal-binding amino acids, combined with peptide macrocyclization using peptide cyclase 1 (PCY1), and shows the resulting cyclic peptides as competent catalysts for metal ligands. The research reveals that PCY1 can tolerate peptides containing amino acids with classic inorganic and organometallic ligands as side chains, paving the way for efficient development of cyclic peptides as metal ligands.
ROYAL SOCIETY OPEN SCIENCE
(2021)
Article
Chemistry, Multidisciplinary
Vincent Boquet, Ali Nasrallah, Alejandro L. Dana, Erwan Brunard, Pablo H. Di Chenna, Fernando J. Duran, Pascal Retailleau, Benjamin Darses, Marie Sircoglou, Philippe Dauban
Summary: C4-symmetrical dirhodium(II) tetracarboxylates are efficient catalysts for the asymmetric intermolecular aziridination of substituted alkenes with sulfamates. The reaction shows high efficiency and chemoselectivity, yielding aziridines with high yields and enantiomeric excesses. It is applicable to various substituted alkenes and the late-stage functionalization of complex substrates.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Applied
Rayhane Hammami, Pascale Maldivi, Christian Philouze, Sebastien Carret, Benjamin Darses, Soufiane Touil, Jean-Francois Poisson
Summary: A variety of 4-phosphinylpyrrolidin-3-ones were synthesized via a [3+2] cycloaddition reaction between aryl aldonitrones and phosphinylallenes. The products were obtained as unique 4,5-trans diastereomers in yields ranging from 47% to 80% for 23 examples. Chiral racemic allenes exhibited a moderate 2:1 to 4:1 2,5-diastereoselectivity. Under the reaction conditions, the cycloadducts undergo a rearrangement to selectively afford the corresponding pyrrolidin-3-ones. DFT calculations provided insights into the mechanism involving the homolytic cleavage of the N-O bond of the cycloadduct.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Thomas Kuckhoff, Richard C. Brewster, Calum T. J. Ferguson, Amanda G. Jarvis
Summary: The design and development of artificial metal-free photoenzymes aim to combine the selectivity of enzymatic reactions with the benefits of modern synthetic photocatalysts. This study presents the design of a novel artificial photoenzyme by integrating an organophotocatalytic moiety into a steroid carrier protein (SCP-2L). The modified photoenzymes showed selectivity for the oxidation of organic sulfides, with up to 192 turnovers.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Sandra Abi Fayssal, Timothee Naret, Vincent Huc, Julien Buendia, Cyril Martini, Emmanuelle Schulz
Summary: The scalable synthesis of Pd-NHC cinnamyl complexes supported on benzyloxycalix[8]arene is reported. These catalysts are highly active for Buchwald-Hartwig cross-coupling reactions, enabling the coupling of aryl chlorides and bromides with alkyl and aryl amines at low catalytic loadings. The supported complexes also produce attractive unsymmetrical triarylamines and can even facilitate the synthesis of unprecedented Pd-catalyzed C-H activation products. Through an easy to implement procedure, these characterized catalysts combine the best features of homogeneous and heterogeneous catalysis, achieving high efficiency and low Pd leaching levels.
CATALYSIS SCIENCE & TECHNOLOGY
(2021)
Article
Chemistry, Multidisciplinary
Axel Labattut, Sandra Abi Fayssal, Julien Buendia, Ibrahim Abdellah, Vincent Huc, Cyril Martini, Emmanuelle Schulz
REACTION CHEMISTRY & ENGINEERING
(2020)
Article
Chemistry, Organic
Maria Ivana Lapuh, Alejandro Dana, Pablo H. Di Chenna, Benjamin Darses, Fernando J. Duran, Philippe Dauban
ORGANIC & BIOMOLECULAR CHEMISTRY
(2019)
