Article
Chemistry, Multidisciplinary
Naveen Diddi, Dale E. Ward
Summary: The total synthesis of dolabriferol C was achieved by a series of unique chemical reactions, simplifying the synthetic process significantly. This synthetic approach combines different stereochemical selectivities and enantioselective reactions, providing new insights for the study of related compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Pier Alexandre Champagne
Summary: The first catalytic intermolecular desymmetrization of azetidines was reported in 2015, and Density Functional Theory calculations were used to uncover the mechanism and high enantioselectivity. The reaction proceeds through bifunctional activation of the azetidine nitrogen and the thione tautomer of the 2-mercaptobenzothiazole nucleophile. The selectivity is driven by the ability of the substrates to fit into the chiral catalyst pocket based on primary orbital interaction requirements.
Article
Chemistry, Multidisciplinary
Fei Xiong, Chao Ma, Yi-Ren Zhu, Chen Sun, Lu Chen, Yan-Jun Zhang, Yuan-Jie Zhu, Zhong-Hua Wang
Summary: A novel thermosensitive bifunctional sulfonamide microgel catalyst, immobilized on a highly cross-linked three-dimensional network structure through covalent interactions, has been successfully used for catalyzing the asymmetric alcoholysis reaction with high yields and good stereoselectivity (up to 90% ee). Furthermore, the polymeric catalysts can be easily recovered and reused multiple times without apparent loss of catalytic activity and enantioselectivity.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Organic
Stefan Malatinec, Eva Bednarova, Hiroki Tanaka, Martin Kotora
Summary: This study presents a catalytic and highly enantioselective ring-opening reaction of epoxides, utilizing newly designed chiral bipyridine ligands. A Sc-complex with a newly developed bipyridine ligand demonstrated high reactivity and stereocontrol in the desymmetrization of meso-epoxides with various alcohols, achieving enantioenriched 1,2-alkoxyalcohols with high e.r. values. Additionally, attempted ring-opening of meso-epoxides with anilines showed lower enantioselectivity, dependent on the electronic effect of substituents on the aromatic ring.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Xiaolei Ji, Chaoren Shen, Xinxin Tian, Kaiwu Dong
Summary: A palladium-catalyzed asymmetric hydroesterification reaction was developed for preparing chiral alpha-substituted succinates with moderate yields and high ee values. The kinetic profile of the reaction progress indicated that the alkene substrate underwent hydroesterification followed by esterification with alcohol. The enantioselectivity was elucidated by density functional theory computation.
Article
Chemistry, Multidisciplinary
Sanjiv O. Tomer, Hemant P. Soni
Summary: In this study, the molecular structure of quinidine was modified and a chiral hemiester catalyst with high enantioselectivity and yield was successfully synthesized.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Organic
Xiufen Bi, Jia Feng, Xiaoping Xue, Zhenhua Gu
Summary: This report describes a rhodium-catalyzed enantioselective ring-opening/acylation of silafluorenes. The use of a newly developed bulky phosphoramidite ligand and methanol additive allows for the generation of one axial chirality and one silicon-stereogenic center with high selectivity by cleaving only one Si-C bond.
Article
Chemistry, Multidisciplinary
Zhi-Kai Zhang, Ya-Li Feng, Zheng Ruan, Yuan-Qing Xu, Zhong-Yan Cao, Meng-Hua Li, Chao Wang
Summary: This article presents a practical method for 1,2-diborylation of non-activated monosubstituted alkenes via nickel catalysis. The method shows high tolerance towards functional groups and can be applied for the synthesis of drugs and modification of natural product derivatives. Preliminary mechanistic studies suggest the involvement of a Ni(ii) catalytic cycle.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Zhifang Chen, Yufeng Zhou, Tingjun Hu, Heng-Ying Xiong, Guangwu Zhang
Summary: This unprecedented 1,3-dipole cycloaddition between acyclic CF3-ketimines and N-benzyl azomethine ylide has been enabled by tungsten catalysis, leading to a range of novel imidazolidines with a trifluoromethylated tetrasubstituted carbon center. The gram-scale synthesis capability and variant derivatizations of cycloaddition adducts demonstrate the synthetic potential of this approach, providing easy access to a rapidly expanding library of motifs with a trifluoromethylated fully substituted carbon.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Junqiang Wei, Vincent Gandon, Ye Zhu
Summary: Synthetic application of asymmetric catalysis requires strategic alignment of bond construction and chiral target molecule creation. Remote desymmetrization offers advantages in spatial decoupling of catalytic transformation and generation of stereogenic element. However, this spatial separation presents challenges for chiral catalysts to discriminate distant enantiotopic sites several bonds away from a prochirality center.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Chemistry, Multidisciplinary
Alexander Sandvoss, Johannes M. Wiest
Summary: Strain relief of oxetanes provides numerous opportunities for synthesizing chiral alcohols and ethers. Enantioselective desymmetrization serves as a powerful tool for constructing molecular complexity through transition metal, Lewis acid, and Bronsted acid catalysis, showcasing the immense possibilities for synthetic application.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Jie Chen, Dong-yu Zhu, Xue-jing Zhang, Ming Yan
Summary: An enantioselective Michael addition has been developed for the synthesis of structurally diverse isatin-derived alpha-(trifluoromethyl)imine derivatives with excellent yields and enantioselectivities, which are valuable candidates for drug discovery.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Xun Zhang, Chengjian Zhang, Xinghong Zhang
Summary: The alternating copolymerization of cyclic acetals and anhydrides can produce biodegradable polyesters with high oxygen content, moderate molecular weight, and narrow polydispersities.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Panxia Zhao, Jie Chen, Nana Ma, Jingfei Chen, Xiangquan Qin, Chuanfei Liu, Fuquan Yao, Lishan Yao, Longyi Jin, Zhiqi Cong
Summary: The study demonstrates the efficient H2O2-dependent (R)-enantioselective epoxidation of unfunctionalized styrene and its derivatives by site-mutated variants of a unique non-natural P450BM3 peroxygenase in combination with a dual-functional small molecule. The synergistic use of protein engineering and an exogenous DFSM represents an effective strategy to control the enantioselectivity of styrene epoxidation, significantly expanding the chemical scope of P450 enzymes as useful bio-oxidative catalysts.
Article
Chemistry, Multidisciplinary
Pinku Tung, Neal P. Mankad
Summary: A light-mediated, Cu-catalyzed process has been developed for directly producing aliphatic, symmetric acid anhydrides from alkyl (pseudo)halides in a single step without the need for precious metal additives. This transformation utilizes simple Cu salts and abundant bases to generate a heterogeneous Cu0 photocatalyst in situ, maintaining high efficiency and selectivity upon scale-up, and operates via a radical mechanism with several advantageous features. This discovery will facilitate the engineering of efficient and sustainable bulk processes for producing commodity anhydrides.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(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)
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
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, 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.
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.
