Article
Chemistry, Organic
Tianxing Qi, Ning Fang, Weimin Huang, Jianhui Chen, Yanshu Luo, Yuanzhi Xia
Summary: An iron(II)-catalyzed nitrene transfer reaction allows for the efficient synthesis of N-acyl sulfoximines with high functional-group compatibility. This catalytic transformation can be conducted under an air atmosphere at ambient temperature and can be scaled up to gram scale.
Article
Chemistry, Organic
Tianxing Qi, Ning Fang, Weimin Huang, Jianhui Chen, Yanshu Luo, Yuanzhi Xia
Summary: An iron(II)-catalyzed nitrene transfer reaction of sulfoxides with N-acyloxyamides has been developed, leading to the efficient construction of N-acyl sulfoximines with high functional-group compatibility. The methodology can be carried out under an air atmosphere at ambient temperature and can be scaled up to gram scale with a catalyst loading of 1 mol %. The application of the methodology was demonstrated by facile C-H acetoxylation and olefination using the N-acyl sulfoximine as the directing group.
Article
Chemistry, Organic
Sonbidya Banerjee, Manmath Mishra, Tharmalingam Punniyamurthy
Summary: In this study, the Cu-catalyzed cross-dehydrogenative coupling of the C7 C-H bond of indolines with sulfoximines has been successfully achieved. The reaction can also be extended to the cross-dehydrogenative coupling of N-aryl 7-azaindoles with monoselectivity. The use of first-row copper catalysis, substrate scope, and late-stage synthetic applications are important practical features of this study.
Article
Chemistry, Physical
Leonardo Massignan, Cuiju Zhu, Xiaoyan Hou, Joao C. A. Oliveira, Aude Salame, Lutz Ackermann
Summary: A new method combining electrosynthesis with non-toxic manganese catalysis was presented for oxidative C-H arylations and C-H alkylations using electricity as the terminal oxidant. Experimental and computational studies confirmed the unique features and reaction mechanism of this method.
Article
Chemistry, Physical
Pu-Fan Qian, Tao Zhou, Jun-Yi Li, Yi-Bo Zhou, Bing-Feng Shi
Summary: Chiral benzothiadiazine-1-oxides are sulfur-stereogenic compounds with structural diversity that have gained significant attention in drug discovery. This study reports the synthesis of these chiral molecules through an asymmetric [4 + 3] annulation reaction of sulfoximines with alpha,beta-unsaturated ketones, catalyzed by an achiral Ru(II) complex and assisted by a chiral carboxylic acid (CCA). The method allows for the preparation of a wide range of chiral benzothiadiazepine-1-oxides with various functional groups in high yields and excellent enantioselectivity, expanding the chemical space of chiral sulfoximines. Importantly, the oxidative cleavage of the products yields chiral N-benzoyl sulfoximines with a C-S chiral axis.
Article
Chemistry, Organic
Bin-Qing He, Yuan Gao, Peng-Zi Wang, Hong Wu, Hong-Bin Zhou, Xiao-Peng Liu, Jia-Rong Chen
Summary: An unprecedented dual photoredox/palladium-catalyzed reaction using oxime esters for C-C bond cleavage and directed ortho C-H acylation of 2-arylpyridines has been described. This redox-neutral protocol demonstrates excellent regioselectivity, broad substrate scope, and good functional-group tolerance, resulting in a range of aryl ketones with generally good yields.
Article
Chemistry, Applied
Yunhao Zhou, Yue Xu, Tao Zheng, Dongliang Huang, Jianyang Chen, Yongchang Wu, Ruhuai Mei, Wenbo Ma
Summary: A copper-mediated C(sp(2))-H chalcogenation of heterocycles using readily available dichalcogenide, benzeneselenol and thiol is reported. This method exhibits scalability, good chemo- and regio-selectivity, as well as broad functional group tolerance, providing an accessible approach for the synthesis of valuable aryl chalcogenides. The chalcogenated picolinamide products can be further transformed into selenoxanthones and thioxanthone scaffolds through intramolecular cyclization via a semi-one pot process.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Shihaozhi Wang, Jiale Yang, Dianjun Li, Jinhui Yang
Summary: A novel tandem N-dealkylation and N-methyl aerobic oxidation of tertiary aromatic amines to N-arylformamides using copper and TEMPO has been developed, providing an alternative synthetic route from N-methylarylamines to N-arylformamides.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yuki Hirata, Daichi Sekine, Yoshimi Kato, Luqing Lin, Masahiro Kojima, Tatsuhiko Yoshino, Shigeki Matsunaga
Summary: In this study, the combination of an achiral cobalt(III) catalyst and a pseudo-C-2-symmetric H-8-binaphthyl chiral carboxylic acid was utilized for the asymmetric synthesis of benzothiadiazine-1-oxides containing a chiral sulfur center. The optimized protocol achieved high enantioselectivity and allowed for the synthesis of benzothiadiazine-1-oxides with various functional groups.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Yang -yang Li, Bing Gao
Summary: N-functionalization of free sulfoximines is a significant method for modifying their properties for various applications. This study presents a rhodium-catalyzed N-allylation of free sulfoximines (=NH) with allenes, enabling chemo- and enantioselective ?-hydroamination of allenes and gem-difluoroallenes. The synthesis of sulfoximine products using this method is also demonstrated.
Review
Chemistry, Organic
Linhao Liu, Manisha Durai, Henri Doucet
Summary: The metal-catalyzed direct functionalization of two different C-H bonds of the same organic molecule, known as regiodivergent C-H bond functionalization, is an important research topic in organic chemistry. The number of tools to control such functionalizations has significantly increased over the last decades, with different metal sources being the most effective. Ru or Rh catalysts can be used for arylation of the aryl unit, while Pd or Cu catalysts can be used for arylation of the azole unit, allowing for regiodivergent direct arylation of aryl-substituted azoles.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Takeru Miyakoshi, Nadja E. Niggli, Olivier Baudoin
Summary: In the past years, Pd-0-catalyzed C(sp(3))-H activation has provided efficient and economical methods for synthesizing carbo- and heterocycles via direct C(sp(2))-C(sp(3)) bond formation. This study reports a 1,4-Pd shift that enables the synthesis of N-heterocycles, which are difficult to build through direct reactions. The reaction involves the 1,4-Pd shift of o-bromo-N-methylanilines at the N-methyl group, followed by intramolecular trapping and remote C-C bond formation, resulting in the formation of biologically relevant isoindolines and beta-lactams. The selectivity of the reaction is influenced by the choice of ligand, with NHCs favoring the formation of products through remote C-C coupling.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Khalid Boujdi, Nabil El Brahmi, Sylvain Collet, Didier Dubreuil, Monique Mathe-Allainmat, Mohamed Akssira, Gerald Guillaumet, Jacques Lebreton, Said El Kazzouli
Summary: A new solvent/ligand-controlled switchable C-H arylation of 1-methyl-4-nitro-1H-indazole catalyzed by Pd(OAc)(2) was achieved. Activation at the C7 position was promoted by a bidentate ligand in DMA, while arylation at the C3 position was directed by a phosphine ligand in H2O. The C3 and C7 arylation products were obtained in moderate to good yields and with high regioselectivity.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Organic
Xiaoqin Ning, Yongke Chen, Fangdong Hu, Ying Xia
Summary: This study presents the palladium-catalyzed cross-coupling reactions of cyclobutanone-derived N-sulfonylhydrazones with aryl or benzyl halides, demonstrating that the metal carbene process and beta-hydride elimination can occur smoothly in strained ring systems to yield structurally diverse products. The preliminary success in asymmetric carbene coupling reactions in strained ring systems offers a promising route for the synthesis of enantioenriched four-membered-ring molecules.
Article
Chemistry, Physical
Jun-Yi Li, Pei-Pei Xie, Tao Zhou, Pu-Fan Qian, Yi-Bo Zhou, Hao-Chen Li, Xin Hong, Bing-Feng Shi
Summary: The Ir(III)-catalyzed asymmetric C-H activation enabled by noncovalent interactions allows for the preparation of a broad range of sulfur-stereogenic sulfoximines with high yields and excellent enantioselectivities. Detailed DFT calculations and experimental studies have shown that the N-H···O hydrogen bonding interaction between sulfoximine and the chiral carboxylic acid ligand is crucial for the high enantiocontrol. Furthermore, chiral iridacycle intermediates have been isolated, characterized, and subjected to stoichiometric reactions, indicating that the C-H cleavage step is the rate- and enantio-determining step.
Article
Chemistry, Physical
Mostafa M. Amer, Rene Hommelsheim, Christian Schumacher, Deshen Kong, Carsten Bolm
Summary: An electro-mechanochemical protocol using strained BaTiO3 nanoparticles has been developed for the synthesis of vinylic sulfoximines. The catalytic active system is generated in situ by the reduction of copper(ii) chloride. The method tolerates various electron-donating and -withdrawing groups, and leads to difunctionalised double bond products in good to excellent yields. Attempts to add a sulfoximidoyl chloride to an alkyne were difficult, while additions of a sulfonyl iodide to allenes and alkynes proceeded smoothly in the presence of silica gel without needing activation by a piezoelectric material.
FARADAY DISCUSSIONS
(2023)
Editorial Material
Chemistry, Physical
Matej Balaz, Viktor Balema, Richard G. Blair, Elena Boldyreva, Carsten Bolm, Adam B. Braunschweig, Robert W. Carpick, Stephen L. Craig, Franziska Emmerling, James P. Ewen, Cecilia Fiore, Tomislav Friscic, Sven Gratz, Ivan Halasz, Ehsan Hamzehpoor, Hajime Ito, Jeung Gon Kim, Giulio Lampronti, Danielle Laurencin, James Mack, Lucia Maini, Paolo P. Mazzeo, Sharmarke Mohamed, Karthik Nagapudi, Allan Niidu, Jogirdas Vainauskas, Caterina Zuffa
FARADAY DISCUSSIONS
(2023)
Editorial Material
Chemistry, Physical
Alexander Angerhofer, Thomas Auvray, Viktor Balema, Matej Balaz, James D. Batteas, Richard G. Blair, Elena Boldyreva, Carsten Bolm, Lars Borchardt, Tristan H. Borchers, Adam B. Braunschweig, Duncan L. Browne, Robert W. Carpick, Maria Ciaccia, Stephen Craig, Franziska Emmerling, Michael Ferguson, Cecilia Fiore, Tomislav Friscic, Sven Gratz, Ivan Halasz, Ehsan Hamzehpoor, Hajime Ito, Stuart James, Jeung Gon Kim, Frederic Lamaty, Giulio Lampronti, Danielle Laurencin, Jamie Leitch, Erli Lu, Stipe Lukin, James Mack, Lucia Maini, Ashlie Martini, Paolo P. Mazzeo, Adam A. L. Michalchuk, Sebastien Mittelette, Sharmarke Mohamed, Audrey Moores, Aldo de Jesus Mortera-Carbonell, Karthik Nagapudi, Allan Niidu, Francesco Puccetti, Martin Stahorsky, Leonarda Vugrin
FARADAY DISCUSSIONS
(2023)
Editorial Material
Chemistry, Physical
Alexander Angerhofer, Matej Balaz, Viktor Balema, Ana M. Belenguer, Richard G. Blair, Elena Boldyreva, Carsten Bolm, Lars Borchardt, Adam B. Braunschweig, Duncan L. Browne, Stephen Craig, Lamis El Wenni, Franziska Emmerling, Michael Ferguson, Cecilia Fiore, Tomislav Friscic, Kimichika Fukushima, Felipe Garcia, Lori Gonnet, Sven Gratz, Rafael A. R. Hernandez, Hajime Ito, Stuart L. James, Deniz Karabiyikli, Jeung Gon Kim, Koji Kubota, Frederic Lamaty, Giulio Lampronti, Jamie Leitch, Stipe Lukin, James Mack, Lucia Maini, Sharmarke Mohamed, Audrey Moores, Karthik Nagapudi, Francesco Puccetti, Mi Tian, Qian Yu
FARADAY DISCUSSIONS
(2023)
Editorial Material
Chemistry, Physical
Matej Balaz, Viktor Balema, James D. Batteas, Richard G. Blair, Carsten Bolm, Lars Borchardt, Adam B. Braunschweig, Stephen L. Craig, Franziska Emmerling, Michael Ferguson, Tomislav Friscic, Stuart James, Jamie Leitch, James Mack, Sharmarke Mohamed, Karthik Nagapudi, Francesco Puccetti, Maria Elena Rivas
FARADAY DISCUSSIONS
(2023)
Article
Chemistry, Organic
Xianliang Wang, Marcus Frings, Kari Rissanen, Carsten Bolm
Summary: N-Alkyl sulfoximines react with in situ generated arynes under mild conditions to afford o-sulfinylanilines in good yields. The transformation exhibits a wide substrate scope and excellent functional group tolerance. The structure of a reaction product was confirmed by single-crystal X-ray diffraction.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Xianliang Wang, Kari Rissanen, Carsten Bolm
Summary: N-Trifluoroacetylated (N-TFA) sulfoximines react with 1-trifluoromethylstyrenes in a one-pot domino reaction to give fluorinated 5,6-dihydro-1,2-thiazine 1-oxides in good to high yields. The process involves three sequential reaction steps that can be characterized as (1) nucleophilic allylic substitution (S(N)2 '), (2) hydrolysis, and (3) intramolecular nucleophilic vinylic substitution (SNV). The products can further be modified by defluorination. The molecular structure of the resulting product was confirmed by X-ray crystallographic analysis.
Article
Chemistry, Multidisciplinary
Marco T. Passia, Mostafa M. Amer, Joachim Demaerel, Carsten Bolm
Summary: A sustainable method for synthesizing sulfur(VI) fluorides using easily available sulfur(VI) 2-methylimidazoles as stable precursors has been developed. The reaction, conducted in a mixer mill under solvent-free conditions with KHF2 as the fluorine source and AcOH as the catalyst, produces sulfonyl, sulfonimidoyl, and sulfoxyl fluorides in good yields. The mechanochemical approach offers shorter reaction times and eco-friendly advantages with simplified purification using silica plug filtration.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Multidisciplinary
Pit van Bonn, Jinbo Ke, Christopher Weike, Jas S. Ward, Kari Rissanen, Carsten Bolm
Summary: Difluoromethyl ethers are obtained through mechanochemical reactions between alcohols and difluorocarbene in a mixer mill. The method is applicable to primary, secondary, and tertiary alcohols, yielding the corresponding products with excellent yields (up to 99%) after 1 hour at room temperature. The reactions take place under solvent-free conditions and the products are purified by filtration, resulting in significantly reduced waste generation.
Review
Chemistry, Multidisciplinary
Igor d'Anciaes Almeida Silva, Ettore Bartalucci, Carsten Bolm, Thomas Wiegand
Summary: Recent studies have shown that mechanochemical strategies are beneficial for directed conversions of organic compounds. However, finding new reactions has been challenging due to the lack of mechanistic understanding of mechanochemical reaction events. Spectroscopic techniques play a crucial role in addressing these questions. In this overview, the opportunities and challenges of solid-state nuclear magnetic resonance (NMR) spectroscopy in the field of organic mechanochemistry are discussed. The strengths of solid-state NMR in ex situ structure characterization, differentiating polymorphs, NMR-crystallographic structure-determination protocols, and detecting weak noncovalent interactions in molecular-recognition events using proton-detected solid-state NMR experiments at fast MAS frequencies are highlighted.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Applied
Rene Hommelsheim, Robin van Nahl, Lena M. Hanek, Jas S. Ward, Kari Rissanen, Carsten Bolm
Summary: This study reports a palladium-catalyzed domino reaction that enables the synthesis of 3-amino-substituted 1,2,4-benzothiadiazine 1,1-dioxides at room temperature. The method demonstrates good substrate compatibility and mild reaction conditions.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Physical
Ettore Bartalucci, Dominique J. Luder, Nicole Terefenko, Alexander A. Malaer, Carsten Bolm, Matthias Ernst, Thomas Wiegand
Summary: Fast MAS NMR experiments have been used to study a wide range of materials, including biomolecules and pharmaceuticals, and proton-spin diffusion (SD) plays a crucial role in resonance assignment and structure determination. Negative cross peaks in 2D SD-based spectra have been observed in small organic molecules with methyl groups, which can be attributed to higher-order coherent contributions dominating the observed negative peaks. The presence of low-frequency shifted H-1 resonances in methyl groups prevents sizeable second-order spin-diffusion processes, masking the negative contribution to the peaks.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Rene Hommelsheim, Sandra Bausch, Robin van Nahl, Jas S. Ward, Kari Rissanen, Carsten Bolm
Summary: A variety of 3-amino-substituted benzothiadiazine oxides were synthesized via a one-step palladium-catalyzed cascade reaction of 2-azido sulfoximines with isonitriles. The desired heterocycles were obtained in good to excellent yields using very low catalyst loadings and short reaction times. This protocol provides direct access to precursors for pharmaceutically relevant sulfoximines.
Article
Hematology
Edouard Lansiaux, Emmanuel Drouin, Carsten Bolm
Summary: Through screening three databases, researchers found that beta-thalassemia carriers may be less affected by COVID-19 than the general population, but they are more likely to experience severe symptoms, have a lower ICU admission rate, and have a higher risk of death. However, these results are not statistically significant, and further large case-control or registry studies are needed to confirm these trends.
THALASSEMIA REPORTS
(2023)
Article
Chemistry, Organic
Carsten Bolm, Xianliang Wang, Kari Rissanen
Summary: N-Trifluoroacetylated sulfoximines react with 1-trifluoromethylstyrenes in a one-pot domino reaction to give fluorinated 5,6-dihydro-1,2-thiazine 1-oxides in good to high yields. The reaction involves nucleophilic allylic substitution, hydrolysis, and intramolecular nucleophilic vinylic substitution. The resulting product's molecular structure was confirmed by X-ray crystallographic analysis.
