Article
Chemistry, Applied
Surajit Duari, Subrata Biswas, Arnab Roy, Srabani Maity, Abhishek Kumar Mishra, Aguinaldo R. Souza, Asma M. Elsharif, Nelson H. Morgon, Srijit Biswas
Summary: In this study, a catalytic synthetic strategy was developed to access various N-functionalized heterocyclic derivatives. The reaction involves the direct nucleophilic substitution of alcohols followed by X to N alkyl group migration. Methyl trifluoromethanesulfonate was found to be an efficient catalyst for this reaction. The mechanism was elucidated through experiments and DFT calculations.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Felipe Ospina, Kai H. Schuelke, Jordi Soler, Alina Klein, Benjamin Prosenc, Marc Garcia-Borras, Stephan C. Hammer
Summary: This study reports a new method for regioselective N-methylation of unsaturated heterocycles. By using two methyltransferases and simple reagents, important molecules with biological activities can be synthesized efficiently.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Johanna Templ, Edma Gjata, Filippa Getzner, Michael Schnuerch
Summary: In this study, we used phenyl trimethylammonium iodide as a reagent to achieve highly selective methylation of amides and indoles. The method is easy to use, provides high yields, has good functional group tolerance, and is particularly suitable for late-stage methylation of bioactive compounds.
Article
Chemistry, Organic
Jianyang Dong, Jianhua Liu, Hongjian Song, Yuxiu Liu, Qingmin Wang
Summary: A mild and operationally simple method using vinyl ethers as acetyl sources for Minisci C-H acetylation of N-heteroarenes is reported. This method does not require conventional photocatalysis, electrocatalysis, metal catalysis, light activation, or high temperature, making it more sustainable in terms of cost, reagent toxicity, and waste generation compared to previous methods. It is expected to obtain medically relevant molecules from abundant feedstock materials.
Article
Chemistry, Organic
Xianqiang Zhong, Guorong Xiao, Wei Zhou
Summary: This study presents a highly efficient method for the addition of Grignard reagents to N-[(o-aminophenyl)methylene]sulfinamides to produce a range of o-aminosulfinylimines with good to excellent diastereoselectivities.
Article
Chemistry, Physical
Prithwish Ghosh, Na Yeon Kwon, Youjung Byun, Neeraj Kumar Mishra, Jung Su Park, In Su Kim
Summary: In this study, a cobalt(II)-catalyzed method for C-H alkylation and acylation of N-heterocycles using 1,4-dihydropyridines (DHPs) as alkylating and acylating agents was reported. The combination of KBrO3 and a Co(II) catalyst successfully generated alkyl and acyl radicals from DHPs. This method was applicable to various heterocycles and demonstrated selectivity in modifying drug candidates and synthesizing bioactive molecules on a gram scale.
Article
Chemistry, Multidisciplinary
Vasco Corti, Mathias Kirk Thaegersen, Valdemar Juel Enemaerke, Nomaan M. Rezayee, Casper L. Barlose, Karl Anker Jorgensen
Summary: The first atroposelective aminocatalytic methodology for the construction of C-N atropisomers is described. By directly coupling indole-2-carboxaldehydes to ortho-quinones, a new library of functionalized and enantioenriched C-N atropisomers was obtained using a designed and synthesized aminocatalyst. The synthetic utility of these atropisomers was demonstrated through various transformations.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Amit Banerjee, Tomohiro Hattori, Hisashi Yamamoto
Summary: In this study, a mild, straightforward, and powerful method for nucleophilic alkylation using trialkyl phosphates is described. The method exhibits high yields and can be applied to a wide range of substrates. Additionally, the inversion of configuration of chiral centers has been achieved.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Multidisciplinary
Laura Santos, Florian Audet, Morgan Donnard, Armen Panossian, Jean-Pierre Vors, David Bernier, Sergii Pazenok, Frederic R. Leroux
Summary: An efficient method for the synthesis of high-value N-polyfluoroalkyl anilines, primary polyfluoroalkylamines, and N,N-bis(polyfluoroalkyl) amines via N-polyfluoroalkylation of sulfonamides and phthalimide derivatives using sulfuryl fluoride (SO2F2) is reported. The in situ formation of polyfluoroalkyl fluorosulfonates from commercially available fluorinated alcohols and economical sulfuryl fluoride is advantageous in terms of environmental impact and cost. This general method allows for the polyfluoroalkylation of a variety of substrates, providing valuable building blocks for life science applications.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Applied
Yong-Xing Song, Da-Ming Du
Summary: The aza-Michael addition cascade reaction is an important synthetic method for constructing functionalized C-N bonds, widely used in the synthesis of chiral drugs, intermediates, and natural products. This review highlights recent developments in asymmetric synthesis, including various types of aza-Michael addition triggered cascade reactions, reaction mechanisms, and derivatization experiments.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Hiroki Tashiro, Masahiro Terada, Itaru Nakamura
Summary: Gold-catalyzed reactions were used to synthesize 2H-azirines with sulfenyl and acyl groups at the 3-position, yielding good to excellent results. These reactions involved internal transfer of sulfinyl oxygen atom and carbene insertion into the N-S bond for ring construction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Jona Merx, Kas J. Houthuijs, Hidde Elferink, Eva Witlox, Jasmin Mecinovic, Jos Oomens, Jonathan Martens, Thomas J. Boltje, Floris P. J. T. Rutjes
Summary: This study characterized cyclic N-acyliminium ions in the gas phase through collision induced dissociation tandem mass spectrometry and infrared ion spectroscopy, providing valuable insights into their conformations through comparison of DFT calculated spectra with experimentally observed IR spectra.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Ziyue Zhu, Vinayak Krishnamurti, Xanath Ispizua-Rodriguez, Colby Barrett, G. K. Surya Prakash
Summary: A straightforward protocol for direct difluoromethylation of specific organic compounds is presented, showing tolerance towards various functional groups. The selectivity of the reaction can be modulated by simple variations in reaction conditions. Gram-scale reactions for preparing difluoromethyl compounds are demonstrated.
Article
Chemistry, Physical
Bo-Han Zhu, Ying-Qi Zhang, Hao-Jin Xu, Long Li, Guo-Cheng Deng, Peng-Cheng Qian, Chao Deng, Long-Wu Ye
Summary: An efficient copper-catalyzed tandem alkyne hydration/intramolecular Mannich reaction has been investigated for the synthesis of valuable compounds. This method allows the efficient synthesis of 3,4-dihydro-2-quinolones with high regio-, diastereo-, and enantioselectivity.
Article
Chemistry, Organic
Zhiqiong Tang, Fang Zhang, Tengfei Yao, Xun-Shen Liu, Yuanyuan Liu, Lu Liu
Summary: This paper presents a dearomative iodocyclization of N-(o-alkynyl)aryl isoindole, which leads to the formation of various biologically active benzoindoleazine skeletons containing alkenyl iodine. The resulting products can undergo further cycloaddition or coupling reactions to form a series of highly functionalized N-fused polycyclic scaffolds.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Xuefeng He, Marie Buchotte, Regis Guillot, Sandrine Deloisy, David J. Aitken
Summary: This study demonstrates the inversion of the diastereoselectivity in a three-component reaction, leading to the synthesis of (2S,3S)-allophenylnorstatin ester derivatives with high anti diastereoselectivity. The procedure presented in this study is one of the most efficient methods to synthesize the title compound to date.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Martha Zoumpoulaki, Gabrielle Schanne, Nicolas Delsuc, Hugues Preud'homme, Elodie Quevrain, Nicolas Eskenazi, Geraldine Gazzah, Regis Guillot, Philippe Seksik, Joelle Vinh, Ryszard Lobinski, Clotilde Policar
Summary: The detection and quantification of exogenous metal complexes are crucial in understanding their activity in complex biological media. This study used ion mobility spectrometry-mass spectrometry (IMS-MS) to demonstrate the intracellular presence and concentration of Mn1 and Mn1P complexes, which are superoxide dismutase (SOD) mimics, in cells.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Sascha Jahnigen, Katia Le Barbu-Debus, Regis Guillot, Rodolphe Vuilleumier, Anne Zehnacker
Summary: In this study, the effect of a twofold screw axis on the solid-state VCD spectrum was investigated using both experimental and theoretical analysis. It was found that the VCD spectrum can reflect the supramolecular chirality of the crystal.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Chanjuan Zhang, Philipp Gotico, Regis Guillot, Diana Dragoe, Winfried Leibl, Zakaria Halime, Ally Aukauloo
Summary: At the core of carbon monoxide dehydrogenase (CODH) active site, two metal ions and hydrogen bonding from amino acids facilitate the interconversion between CO2 and CO. A designed molecular catalyst with a bimetallic iron complex and hydrogen bonding interactions showed improved selectivity and stability in heterogeneous CO2 reduction to CO. X-ray structures revealed the compromise between rigidity and flexibility of the catalyst in accommodating CO2 capture, activation, and reduction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Audrey Mauger, Maxime Jarret, Aurelien Tap, Remi Perrin, Regis Guillot, Cyrille Kouklovsky, Vincent Gandon, Guillaume Vincent
Summary: We synthesized highly strained pentacyclic caged framework of mavacuran alkaloids and successfully achieved the concise total synthesis of C-fluorocurine, C-profluorocurine, C-mavacurine, normavacurine, 16-epi-pleiocarpamine and taberdivarine H. A strategy involving late-stage Michael addition and intermolecular 1,4-addition reactions was designed. The first total syntheses of C-profluorocurine and C-fluorocurine were achieved through dihydroxylation of C-mavacurine and a pinacol rearrangement, respectively.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Yuna Kim, Clemence Allain, Regis Guillot, Pierre Audebert
Summary: This article describes a tetrazine derivative that exhibits color-tunable crystals upon external stimuli. By heating and cooling processes, Bis(4-methylphenoxy)tetrazine (1) forms crystalline phases with photoluminescence color transitions ranging from green to red. These thermoresponsive polymorphisms and colors can be reversibly recovered by solvent vapor annealing. Additionally, the unique T-shape arrangement of the tetrazine rings and the phenyl rings leads to the formation of flexible crystals.
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
(2023)
Article
Chemistry, Organic
Dayi Liu, Zeynab Imani, Catherine Gourson, Regis Guillot, Sylvie Robin, David J. J. Aitken
Summary: Post-synthetic modification is a powerful technique for accessing noncanonical peptide derivatives selectively, but it has not been used for installing multiple arrays of modified side chains. In this study, we applied this approach in solution phase to prepare short N- and C-capped homooligomers of 3-amino-1-methylazetidine-3-carboxylic acid with all azetidine side chain functions in the free amine form. The key step involved multiple reductive amination reactions of the corresponding post-synthetically deprotected secondary amines.
Article
Chemistry, Inorganic & Nuclear
Roxanne Bercy, Jean-Noel Rebilly, Christian Herrero, Regis Guillot, Helene Maisonneuve, Frederic Banse
Summary: In this study, three new iron complexes with amine/pyridine ligands were designed and used as catalysts for the oxidation of small organic molecules by hydrogen peroxide. The addition of acetic acid was found to significantly enhance the efficiency of these catalytic systems. Acetic acid promoted the protonation/dissociation of the ligands and the formation of more efficient intermediates.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Cyrille Kouklovsky, Erwan Poupon, Laurent Evanno, Guillaume Vincent
Summary: In this paper, we reported on our efforts towards the total synthesis of mavacuran alkaloids and their highly natural complex bis-indoles. Through a combination of bioinspired and non-bioinspired synthetic routes, we successfully synthesized several mavacuran alkaloids.
Article
Chemistry, Organic
Dayi Liu, Regis Guillot, Sylvie Robin, David J. Aitken
Summary: In this study, trans-3-benzyloxycarbonylamino-1-methyl-3-(methylcarbamoyl)azetidine-1-oxide was successfully synthesized by stereoselective oxidation. The stable molecule was characterized in solution and solid state, revealing different intramolecular and intermolecular hydrogen bonding patterns.
Article
Chemistry, Inorganic & Nuclear
Diana Cebotari, Sergiu Calancea, Jerome Marrot, Regis Guillot, Clement Falaise, Vincent Guerineau, David Touboul, Mohamed Haouas, Aurelian Gulea, Sebastien Floquet
Summary: This paper reports the synthesis and characterization of six coordination complexes obtained by reacting [MoV2 O2S(2)](2+) clusters with bisthiosemicarbazone ligands containing flexible or rigid spacers. The nuclearity of the complexes was found to be controlled by the nature of the spacer between the thiosemicarbazone units, as revealed by structural characterization techniques. Flexible spacers resulted in binuclear complexes [MoV2 O2S2(L1-3)], while rigid spacers led to tetranuclear complexes [(MoV2 O2S2)(2)(L4-6)(2)].
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Shanyu Tang, Guillaume Vincent
Summary: We have developed a convergent paired electrolysis method for the arylative functionalization of a benzylic C(sp(3))-H bond. This process involves the coupling of a benzylic radical or carbocation with a 1,4-dicyanoarene radical anion to form the desired C-C bond. One of the challenges overcome was preventing the formation of overoxidized coupling products at the bisbenzylic position.
Article
Chemistry, Inorganic & Nuclear
Jean-Noel Rebilly, Christian Herrero, Katell Senechal-David, Regis Guillot, Frederic Banse
Summary: The catalytic properties of an iron complex with a pentadentate cross-bridged ligand backbone were investigated. It exhibited moderate conversions in epoxidation and alkane hydroxylation with H2O2 as the oxidant, and satisfactory conversions in aromatic hydroxylation. However, the addition of acid to the reaction medium significantly enhanced the oxidation of aromatics and alkenes. Spectroscopic analysis revealed that the accumulation of the expected Fe-III(OOH) intermediate was limited under these conditions, unless an acid was present, which was attributed to the inertness induced by the cross-bridged ligand backbone that was partly reduced under acidic conditions.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Organic
Nabila Braia, Mounia Merabet-Khelassi, Martial Toffano, Regis Guillot, Louisa Aribi-Zouioueche
Summary: In this paper, we report the highly selective ring opening of a biobased itaconic anhydride catalyzed by Pseudomonas cepacia lipase at room temperature. This method is efficient and environmentally friendly, allowing for the synthesis of valuable itaconate esters using a variety of alcohols as nucleophiles. The reaction yields novel itaconate products when achiral primary alcohols are used as substrates.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
