Article
Chemistry, Multidisciplinary
Junjie Meng, Hui He, Qianru Liu, Hanhong Xu, Huicai Huang, Shao-Fei Ni, Zhaodong Li
Summary: A PdII-catalyzed domino enantioselective desymmetrizative coupling of 7-azabenzonorbornadienes with alkynylanilines is described, which generates valuable functionalized compounds with excellent enantio- and diastereo-selectivity. The method allows the construction of multiple covalent bonds and stereocenters in an efficient and atom-economical manner.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Ferran Planas, Matteo Costantini, Marc Montesinos-Magraner, Fahmi Himo, Abraham Mendoza
Summary: The study found that the slower dimerization reaction of NHPI-DA catalysis led to better selectivity; calculations showed multiple reaction pathways for the cyclopropanation of NHPI-DA, with carbene insertion being a key step; the stereoselectivity of the reaction depends on the intricate balance between various mechanistic scenarios.
Article
Biochemistry & Molecular Biology
Kosuke Yamamoto, Keisuke Miyamoto, Mizuki Ueno, Yuki Takemoto, Masami Kuriyama, Osamu Onomura
Summary: In this study, glycerol was efficiently transformed into optically active monosulfonylated glycerol using a specific catalyst system. The synthetic utility of the monosulfonylated glycerol was demonstrated by its transformation into a C3 unit with differentially protected three hydroxy moieties.
Article
Chemistry, Physical
Kai-Lin Yin, Shuang Zhao, Ying Qin, Shu-Han Chen, Bo Li, Dongbing Zhao
Summary: A carbon-to-silicon switch is widely used in drug discovery. However, organosilicon compounds are not naturally occurring, so the development of effective synthetic methods is crucial for expanding their diversity. In this study, we have successfully synthesized a chiral bridged bicyclic silicon scaffold, which provides a new approach for the synthesis of chiral silicon compounds.
Article
Chemistry, Multidisciplinary
Mingxin Liu, Nguyen Le, Christopher Uyeda
Summary: Nickel catalysts promote nucleophilic cyclopropanation reactions using CH2Cl2 as a methylene source and Mn as a stoichiometric reductant. The substrate scope includes a broad range of alkenes bearing electron-withdrawing substituents, and enantioselective cyclopropanations have been developed using chiral PyBox ligands. Mechanistic studies suggest the intermediacy of a (PyBox)Ni=CH2 species and DFT models provide a rationale for the nucleophilic character of the nickel carbene and the sense of enantioinduction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Johannes Grosskopf, Thorsten Bach
Summary: Upon irradiation with a suitable chiral catalyst, racemic compounds can be converted into enantiopure compounds through a process called photochemical deracemization. This review comprehensively covers the research and current developments in this field, discussing the reactions and mechanistic details underlying the presented reaction. Photochemical deracemization offers a unique opportunity to directly obtain enantiopure compounds from racemates, and short-lived intermediates play a key role in determining the enantioselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
David McLeod, Nicolaj Inunnguaq Jessen, Thanh V. Q. Nguyen, Marcus Espe, Jeremy David Erickson, Karl Anker Jorgensen, Limin Yang, K. N. Houk
Summary: An unusual diastereodivergent stereoselective allylation reaction is presented, where the diastereoselectivity is controlled by the electronic properties of a monodentate, achiral ligand on palladium. This method enables the synthesis of highly stereoselective products.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Min Zhu, Martin Oestreich
Summary: A group-selective monosilylation of silanediols using List's counteranion-directed silylation methodology is described. The enantioselectivity is achieved by generating a silylium-ion-like silicon electrophile from an allylic silane paired with an imidodiphosphorimidate (IDPi), enabling discrimination of the two hydroxy groups attached to the prochiral silicon atom. Furthermore, the enantioselectivity is improved by a subsequent kinetic resolution, resulting in silicon-stereogenic disiloxanes with high enantiocontrol.
Review
Chemistry, Multidisciplinary
Corinne Coutant, Paul De Bonfils, Pierrick Nun, Vincent Coeffard
Summary: The advent of asymmetric organocatalysis has revolutionized the way chemists create or break chemical bonds, enabling new strategies for enantioselective functionalization. This success is attributed to various activation modes and the availability of numerous chiral organic catalysts. Selective functionalization of compounds with multiple activation sites, such as cyclohexanone-derived dienones, has also contributed to breakthroughs in this field. These compounds can undergo diverse transformations and offer new opportunities for natural product synthesis. This review focuses on intermolecular functionalization of (cross)-conjugated cyclohexanone-derived compounds using asymmetric organocatalysis.
Article
Chemistry, Multidisciplinary
Soumen Barik, Sayan Shee, Soumik Das, Rajesh G. Gonnade, Garima Jindal, Subrata Mukherjee, Akkattu T. Biju
Summary: This study describes the atroposelective synthesis of N-aryl succinimides with axially chiral C-N bonds catalyzed by N-heterocyclic carbenes, achieving good yields and ee values. Preliminary investigations were also conducted on the rotation barrier for the C-N bond, temperature dependence, and detailed DFT studies on the mechanism.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Yu Zhanglong, Li Zhongliang, Yang Changjiang, Gu Qiangshuai, Liu Xinyuan
Summary: This review summarizes the research progress in copper-catalyzed enantioselective desymmetrization of diols, and provides a brief perspective on its application prospects in medicinal chemistry, total synthesis, and materials science.
ACTA CHIMICA SINICA
(2023)
Article
Chemistry, Multidisciplinary
Jia-Le Xie, Zheng Xu, Han-Qi Zhou, Yi-Xue Nie, Jian Cao, Guan-Wu Yin, Jean-Philippe Bouillon, Li-Wen Xu
Summary: The study presents a highly enantioselective hydrosilylation of ynones using a palladium catalyst with a chiral ligand, leading to the formation of a series of silicon-stereogenic silylenones with high yield and enantioselectivity. The reaction mechanism and origin of high degree of stereoselectivity were elucidated through density functional theory calculations, highlighting the importance of aromatic interactions in the reaction.
SCIENCE CHINA-CHEMISTRY
(2021)
Article
Chemistry, Physical
Dekun Zhang, Ying-Bo Shao, Wansen Xie, Yunrong Chen, Wei Liu, Hanyang Bao, Faqian He, Xiao-Song Xue, Xiaoyu Yang
Summary: In this paper, a remote enantioselective desymmetrization protocol for asymmetric aromatic aminations of 9,10-dihydroacridines is disclosed. A new spirocyclic chiral phosphoric acid (CPA) catalyst is used to achieve this synthesis, leading to a wide range of chiral dihydroacridines with excellent enantioselectivities. This method is also applicable in the construction of stereogenic silicon center and kinetic resolution of unsymmetrical dihydroacridine derivatives. Density functional theory calculations elucidate the origin of the reactions' excellent regio- and enantioselectivity.
Article
Chemistry, Physical
Chuncheng Zou, Lei Yang, Lei Zhang, Chengyu Liu, Yueyue Ma, Gonghua Song, Zhen Liu, Ruihua Cheng, Jinxing Ye
Summary: The study introduces a method for the synthesis of chiral all-carbon spirocycles catalyzed by a silver(I)/bisdiamine complex, with DFT calculations confirming its high catalytic activity and enantioselectivity. Additionally, various polycyclic products can be obtained through derivatization of the spirocyclic enones.
Article
Chemistry, Multidisciplinary
Rie Yoshimoto, Attila Taborosi, Qiyuan He, Yusuke Ano, Naoto Chatani, Seiji Mori
Summary: The reaction between aromatic amides and maleimides, catalyzed by palladium, leads to the formation of a product with double C-H bond activation, occurring at both the benzylic and meta positions. Computational chemistry studies reveal a stepwise mechanism involving a six-membered palladacycle, maleimide insertion, protonation of the Pd-N bond, and activation of the meta C-H bond. The site selectivity is determined by the interaction energy controlling the insertion of maleimide into the Pd-C(sp(3)) bond. The meta C-H bond activation step is identified as the rate-determining step based on the energetic span model. The 2-thiomethylphenyl group is found to function effectively as a directing group due to strong Pd-S bonding and the destabilizing effect of the deformation energy.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Organic
Christian Schumacher, Jas S. Ward, Kari Rissanen, Carsten Bolm, Mohamed Ramadan El Sayed Aly
Summary: Cholesterol can react under Appel conditions to form 3,5-cholestadiene and 313-bromocholest-5-ene, which deviates from the stereochemistry of the standard Appel mechanism due to the involvement of A5 pi-electrons. However, the subsequent azidolysis of 313-bromocholest-5-ene proceeds mainly by Walden inversion, resulting in the formation of 3a-azidocholest-5-ene. The structures of the products were confirmed by X-ray crystallography and the NMR data matched the reported data.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Rene Hommelsheim, Sandra Bausch, Arjuna Selvakumar, Mostafa M. Amer, Khai-Nghi Truong, Kari Rissanen, Carsten Bolm
Summary: Copper(I)-catalyzed domino reactions of 2-azido sulfoximines with 1-iodoalkynes afford fused triazolyl-containing benzothiadiazine-1-oxides in one step with high yields. This method exhibits broad functional group tolerance and allows the synthesis of two fused heterocyclic rings. Mechanistic investigations reveal the involvement of a copper pi-complex and an iodinated triazole intermediate in the reaction sequence.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Ettore Bartalucci, Christian Schumacher, Leeroy Hendrickx, Francesco Puccetti, Igor d'Anciaes Almeida Silva, Riza Dervisoglu, Rakesh Puttreddy, Carsten Bolm, Thomas Wiegand
Summary: Mechanical forces, including compressive stresses, have a significant impact on chemical reactions. The absence of organic solvents, synthetic acceleration, and unique reaction pathways make mechanochemical conditions advantageous. An accurate characterization of ball-milling products and a deeper mechanistic understanding of the transformations at a molecular level are critical for fully realizing the potential of organic mechanosynthesis.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
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)
Article
Chemistry, Multidisciplinary
Pierre Quinodoz, Alexandre Lumbroso, Mathilde Lachia, Claudio Screpanti, Stefano Rendine, Beyza Horoz, Mert Bozoflu, Saron Catak, Raymonde Fonne-Pfister, Katrin Hermann, Alain De Mesmaeker
Summary: A new class of signaling molecules called strigolactams has been discovered, showing strong potential to induce the germination of the parasitic weed O. cumana and displaying enhanced chemical and soil stability. The stereoselective synthesis of these strigolactams has been achieved, which highlights the significant influence of stereochemistry on compound activity. Stability studies in soil reveal that stereoisomers have different degradation kinetics, emphasizing the importance of stereochemistry.
HELVETICA CHIMICA ACTA
(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
Masahiko Yoshimura, Pierre Quinodoz, Lucia Reyes Mendez, Amandine Kolleth, Sarah Sulzer-Mosse, Thomas Vent-Schmidt, Ulfet Karadeniz Yezer, Saron Catak, Alain De Mesmaeker
Summary: Polycyclic aromatic hydrocarbons (PAHs) are important molecules in science and technology. Amino-substituted PAHs have potential for use in materials science. However, current synthetic methods limit the diversity of amino-substituted PAH structures.
HELVETICA CHIMICA ACTA
(2023)
Article
Engineering, Chemical
Idil I. Demiralp, Ipek Azizoglu, A. Barkin Cimen, Mert Haktanir, Seda Karahan, Zeynep Pinar Haslak, Viktorya Aviyente
Summary: Highly acidic crude oils are considered as good alternatives to typical crude oils for transportation fuels, but their corrosion poses a major concern. This study uses quantum mechanical tools to understand the unimolecular decomposition of carboxylic acids and naphthenic acids (NAs). The results reveal the effects of temperature and other factors on the decomposition process, which can help optimize the processes and provide reaction rates for kinetic models.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(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
Chemistry, Organic
Semiha Kevser Bali, Zeynep Pinar Haslak, Gulsah Cifci, Viktorya Aviyente
Summary: The human topoisomerase IB enzyme relaxes supercoils on double-stranded DNA by forming a covalent DNA/hTopoIB complex. Inhibition of hTopoIB results in cell death, making it a potential target for cancer treatment. Different inhibitors, such as CPT and IQN, have shown different preferences for DNA bases when bound to the DNA/hTopoIB complex. This study investigates the affinities of CPT and an IQN derivative to different DNA base pairs, providing insights for designing gene-specific and more potent compounds to combat cancer through hTopoIB poisoning.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
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, Physical
Aslihan Hepguler, Pelin Ulukan, Saron Catak
Summary: In this study, the thermally activated delayed fluorescence (TADF) properties of emitters with sulfone-based acceptor moieties were investigated using density functional theory (DFT) methods. The focus was on three important structural parameters that affect the efficiency of intersystem crossing (ISC) and reverse intersystem crossing (RISC).
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
