Article
Chemistry, Organic
Xiaoli He, Jiahao Ling, Zhixing Fang, Lei Zhou
Summary: A dual C-F bond cleavage of alpha-CF3-ortho-hydroxystyrenes triggered by alkyl radicals was developed for the synthesis of 2-fluorobenzo-furans. The visible-light-induced defluorinative cross-coupling reactions of alpha-CF3-ortho-hydroxystyrenes with various carboxylic acids produced gem-difluoroalkenes, which underwent SNV-type 5-endo-trig cyclization to give 2-fluorobenzo-furans. Mechanistic studies revealed that electron transfer between phenoxyl radicals and carboxylates was the main pathway for alkyl radical generation.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Applied
Ken Okuno, Bun Chan, Seiji Shirakawa
Summary: Catalytic kinetic resolution is a reliable method for enantioselective synthesis of chiral molecules. However, it is challenging to perform kinetic resolution on racemic compounds with similar substituents at a chiral center. In this study, a kinetic resolution of a-allyl-a-propargyl carboxylic acids was achieved using a chiral bifunctional sulfide catalyst. The utility of the resulting optically active compounds was also demonstrated.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Ken Okuno, Yasuaki Furuya, Seiji Shirakawa
Summary: The kinetic resolution of racemic compounds is a reliable method to prepare chiral molecules in highly optically enriched forms. However, the kinetic resolution of racemic carboxylic acids has not been well developed. Esterification and lactonization promoted by chiral organocatalysts have been found to be effective methods for the kinetic resolution of chiral carboxylic acids.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Andrey Shatskiy, Anton Axelsson, Elena V. Stepanova, Jian-Quan Liu, Azamat Z. Temerdashev, Bhushan P. Kore, Bjorn Blomkvist, James M. Gardner, Peter Diner, Markus D. Karkas
Summary: A protocol for stereoselective C-radical addition to a chiral glyoxylate-derived N-sulfinyl imine was developed through visible light-promoted photoredox catalysis, providing a convenient method for the synthesis of unnatural alpha-amino acids. The protocol allows the use of ubiquitous carboxylic acids as radical precursors without prior derivatization. Alternative mechanisms for the developed transformation are discussed and corroborated by experimental and computational studies.
Article
Chemistry, Organic
Akira Matsumoto, Zhe Wang, Keiji Maruoka
Summary: A new approach for ester activation via a radical-mediated process enabled by a copper/Selectfluor system is described here. This method allows for the conversion of para-methoxybenzyl esters into acyl fluorides, which can be directly used in the one-pot synthesis of amides and peptides. The method has been successfully applied to the iterative formation of sterically hindered amide bonds as a proof of concept.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Yumeng Liang, Zhengyu Zhao, Akihito Taya, Norio Shibata
Summary: A novel reagent system allows for the direct synthesis of acyl fluorides from carboxylic acids, aldehydes, or alcohols with high yields up to 99%. This transformation is useful for late-stage functionalization of natural products and drug molecules containing a carboxylic acid, aldehyde, or alcohol group.
Letter
Chemistry, Organic
Matthew C. Leech, Dmitrii Nagornii, Jamie M. Walsh, Cyrille Kiaku, Darren L. Poole, Joseph Mason, Iain C. A. Goodall, Perry Devo, Kevin Lam
Summary: A practical electrochemical method for the synthesis of tertiary hindered alkyl fluorides from carboxylic acids is developed, which is rapid, safe, and mild without the need for hydrofluoric acid salts or non-glass reactors. Collidinium tetrafluoroborate acts as both the supporting electrolyte and fluoride donor in this anodic fluorination. The compatibility of a wide range of functional groups and the potential for scale-up using flow electrochemistry are demonstrated.
Article
Chemistry, Organic
Xiaojian Jiang, Xi Xu, Wei Xu, Pei Yu, Ying-Yeung Yeung
Summary: A catalytic asymmetric halocyclization protocol was developed for the synthesis of benzoxazepinones and benzoxazecinones using (DHQ)(2)PHAL as the catalyst. Excellent yields and enantioselectivities were achieved under mild conditions. The cocrystal structure of the substrate and the catalyst was studied to provide insights into the reaction mechanism.
Article
Chemistry, Multidisciplinary
Janardana Reddi Desireddi, Mora Mallikarjuna Rao, Kiran Kumar Murahari, Rajashekar Reddy Nimmareddy, Thirupathi Mothe, Arun Kumar Lingala, Bhimcharan Maiti, Ravinder Manchal
Summary: Efficient and facile synthesis of Japanese orange fly lactone was achieved from a commercially available D-glucose. The study discovered the beta-oxygen effect in the deoxygenation step and provided opportunities for further biological studies of this natural product and the development of potentially promising pheromones.
Article
Chemistry, Organic
Feng Jiang, Tengfei Meng, Ying Zhou, Zhenying Xiong, Yupei Zhao, Wengang Guo
Summary: We report an enantio- and diastereodivergent synthesis of enantioenriched fluorenes with broad substrate scope and high enantioselectivity (up to 99% ee) under low catalyst loading (0.1 mol %). The success of this method lies in the pseudo-diastereodivergent desymmetrization of stereoisomers of meso-epoxides enabled by the same organocatalyst. Furthermore, some of the chiral fluorenes obtained exhibit high fluorescence quantum yields (up to 76.6%), as evidenced by photophysical properties studies.
Article
Chemistry, Organic
Keisuke Takahashi, Shunya Kudo, Kiharu Kawamura, Taichi Kusakabe, Shoko Kikkawa, Isao Azumaya, Keisuke Kato
Summary: The proposed structure of mohangic acid C (3) was synthesized through a series of reactions, which selectively introduced specific functional groups and constructed the overall framework of the molecule.
Article
Chemistry, Organic
Boxiang Liu, Zhicong Lin, Tairan Cheng, Tongxiang Cao, Shifa Zhu
Summary: In this study, a highly atom- and step-economical stereoselective synthesis of E-dienyl esters is reported. This approach involves rhodium catalysis and utilizes carboxylic acid and acetylene as C2 synthon through a cascade of cyclometalation and C-O coupling. The protocol demonstrates mild conditions, excellent functional group tolerance, exclusive E-stereoselectivity, and proves useful for late-stage modification of pharmaceuticals and natural products.
Article
Chemistry, Multidisciplinary
Xiao-Qiang Hu, Zi-Kui Liu, Ye-Xing Hou, Guodong Zhang, Yang Gao
Summary: An unprecedented ruthenium catalysed [4+4] annulation of readily available benzoic acids and alkynes has been reported, allowing for the efficient synthesis of a wide array of eight-membered lactones under oxidant-free conditions. The carboxylate group serves as both a directing group and an internal nucleophilic reagent to facilitate the reaction.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Jiang-Lin Hu, Felix Bauer, Bernhard Breit
Summary: A novel ruthenium-catalyzed synthetic method for branched allylic esters via addition of carboxylic acids to allenes was reported in this study. Ligands based on the Josiphos skeleton were designed and prepared, achieving high yield and high enantiomeric excess. Deuterium labeling experiment was conducted to propose a plausible mechanism, and enantiopure lactones of five- and six-membered ring were synthesized through a RCM reaction of the branched allylic ester product.
Article
Chemistry, Organic
Yinrong Wu, Lu Li, Kangmei Wen, Jie Deng, Jiewen Chen, Jie Shi, Ting Wu, Jianxin Pang, Xiaodong Tang
Summary: A copper-catalyzed C-3 functionalization of imidazo[1,2-a]pyridines with 3-indoleacetic acids has been developed, providing a series of compounds with potent antiproliferative activity in cancer cell lines under simple reaction conditions.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Zheng-Jia Shen, Chen Zhu, Xiao Zhang, Chao Yang, Magnus Rueping, Lin Guo, Wujiong Xia
Summary: This article describes a selective (deutero)hydrodefluorination reaction via electrolysis, which achieves remarkable chemoselectivity control by the addition of different organoboron sources. The method is operationally simple, scalable, and provides access to high-value building blocks for medicinal chemistry in one step.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Jose J. Delgado-Marin, Alejandra Rendon-Patino, Vijay Kumar Velisoju, Gadde Sathish Kumar, Naydu Zambrano, Magnus Rueping, Jorge Gascon, Pedro Castano, Javier Narciso, Enrique V. Ramos-Fernandez
Summary: We demonstrate that ZIFs used as catalysts for CO2 insertion suffer from irreversible degradation by leaching, leading to decreased stability and catalytic activity. Additional treatments are necessary to improve their stability.
CHEMISTRY OF MATERIALS
(2023)
Article
Materials Science, Multidisciplinary
Jean Michel Merkes, Gerhard Raabe, Fabian Kiessling, Magnus Rueping, Srinivas Banala
Summary: The isolation and characterization of a kinetically stable oxadiazaborinine (ODB) dye are described in this study. It undergoes an unexpected thermal boron rearrangement, which results in a color change and increased fluorescence. This controllable reaction allows for the practical use as a time-temperature indicator probe, offering advantages such as photostability, non-reversibility, and environmental friendliness.
ADVANCED OPTICAL MATERIALS
(2023)
Editorial Material
Multidisciplinary Sciences
Huifeng Yue, Chen Zhu, Magnus Rueping
Article
Nanoscience & Nanotechnology
David Ohayon, Dominik Renn, Shofarul Wustoni, Keying Guo, Victor Druet, Adel Hama, Xingxing Chen, Iuliana Petruta Maria, Saumya Singh, Sophie Griggs, Bob C. Schroeder, Magnus Rueping, Iain McCulloch, Sahika Inal
Summary: We developed an electrochemical transistor with an n-type conjugated polymer film for sensitive and selective glucose detection in bodily fluids. By studying the impact of the polymer chemical structure on film surface properties and enzyme adsorption behavior, we found that a negatively charged, smooth, and hydrophilic film surface provides the best environment for enzyme adsorption and maximizes sensor performance.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Saidkhodzha Nematulloev, Arunachalam Sagadevan, Badriah Alamer, Aleksander Shkurenko, Renwu Huang, Jun Yin, Chunwei Dong, Peng Yuan, Khursand E. Yorov, Azimet A. Karluk, Wasim J. Mir, Bashir E. Hasanov, Mohamed Nejib Hedhili, Naveen M. Halappa, Mohamed Eddaoudi, Omar F. Mohammed, Magnus Rueping, Osman M. Bakr
Summary: This study reports the synthesis of atomically precise copper hydride nanoclusters with a controlled defect, which were demonstrated to be highly selective catalysts for C-C cross-couplings. The work highlights the potential of defective nanoclusters as model systems for investigating individual defects, correlating defects with physicochemical properties, and rationally designing new nanoparticle catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Haifeng Chen, Chen Zhu, Huifeng Yue, Magnus Rueping
Summary: In this study, a nickel-catalyzed, three-component reductive protocol for group 14 element hetero-difunctionalization of 1,3-enynes using electrochemistry is described. The method is mild, selective, and general, allowing for the silyl-, germanyl-, and stannyl-alkylation of enynes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Serik Zhumagazy, Chen Zhu, Huifeng Yue, Magnus Rueping
Summary: This article describes a nickel-catalyzed C-Se cross-coupling reaction between aryl iodides and selenols. The newly developed catalytic methodology provides easy access to various asymmetric selenium-containing compounds. The reaction exhibits excellent functional group tolerance, a wide range of substrates, high efficiency, and operates under mild conditions. Importantly, the protocol can be readily scaled up to gram-scale reactions without a loss of yield.
Article
Multidisciplinary Sciences
Liuzhuang Xing, Qian Yang, Chen Zhu, Yilian Bai, Yurong Tang, Magnus Rueping, Yunfei Cai
Summary: In this study, the authors successfully incorporated privileged homogeneous bipyridyl-based Ni-catalysts into highly ordered and crystalline potassium poly(heptazine imide) (K-PHI), achieving the development goal of heterogeneous metallaphotocatalysis. The LnNi-PHI catalysts exhibit superior chemical stability and recyclability in C-P, C-S, C-O and C-N cross-coupling reactions.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Gadde Sathish Kumar, Chen Zhu, Rajesh Kancherla, Prashant S. S. Shinde, Magnus Rueping
Summary: An efficient method for the reductive cross-electrophile coupling of aziridines with aryl halides using nickel electrocatalysis is reported. Valuable phenethylamines are synthesized at room temperature in good yields. The reaction is distinct from conventional and photochemical couplings, and the role of Ni(II) organometallic complexes and electrodes in the reaction mechanism are examined.
Review
Chemistry, Physical
Sam Mathew, Dominik Renn, Magnus Rueping
Summary: Amine transaminases play a crucial role in the synthesis of chiral amines, which are essential building blocks in pharmaceuticals and fine chemicals. Advances in enzyme discovery, process engineering, and protein engineering have significantly enhanced the use of transaminases in organic synthesis. Enzymatic cascade engineering has emerged as an efficient and environmentally friendly approach for chiral amine synthesis, allowing the generation of valuable products from inexpensive starting materials. This review focuses on the utilization of amine transaminases in enzymatic and chemoenzymatic cascades for chiral amine synthesis.
Article
Chemistry, Physical
Haifeng Chen, Chen Zhu, Huifeng Yue, Magnus Rueping
Summary: An efficient cobalt-catalyzed carbon-germanium bond formation method has been developed, providing access to a wide range of functionalized germane-containing compounds. This method shows a broad scope and good tolerance toward various functional groups, and is conducted under mild reaction conditions. Mechanistic studies shed light on the unexpected reaction pathway and sequential activation of different electrophiles.
Article
Biotechnology & Applied Microbiology
Ram Karan, Dominik Renn, Shuho Nozue, Lingyun Zhao, Satoshi Habuchi, Thorsten Allers, Magnus Rueping
Summary: This study presents a genetic engineering and chemical modification approach to functionalize the major gas vesicle nanoparticle (GVNP) protein, GvpA. By introducing combinatorial cysteine mutagenesis within GvpA and expanding the N- and C-terminal regions, GvpA single, double, and triple cysteine variant libraries were generated. Thiol-maleimide chemistry was used to introduce biotechnologically relevant activities to the GVNPs. This approach significantly expands the bioengineering and functionalization potential of these novel protein nanomaterials.
JOURNAL OF NANOBIOTECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Wenhuan Huang, Chenyang Su, Chen Zhu, Tingting Bo, Shouwei Zuo, Wei Zhou, Yuanfu Ren, Yanan Zhang, Jing Zhang, Magnus Rueping, Huabin Zhang
Summary: The solar-driven evolution of hydrogen from water using particulate photocatalysts is a promising method for achieving a stable supply of renewable energy. However, the efficiency of photocatalytic water splitting is low due to sluggish electron-hole pair separation kinetics. In this study, highly oxidized Mo species incorporated into Cd0.5Zn0.5S nanorods exhibit significantly enhanced photocatalytic efficiency through inhibited electron-hole recombination.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Chunwei Dong, Ren-Wu Huang, Arunachalam Sagadevan, Peng Yuan, Luis Gutierrez-Arzaluz, Atanu Ghosh, Saidkhodzha Nematulloev, Badriah Alamer, Omar F. Mohammed, Irshad Hussain, Magnus Rueping, Osman M. Bakr
Summary: In this study, a synthesis method for obtaining an atomically precise nanoparticle with a surface-defective analogue is reported. The loss of a single surface atom drastically alters the reactivity of the nanoparticle, showing promising activity for click chemistry, especially photoinduced azide-alkyne cycloaddition. This study not only uncovers the effect of single-surface atom modification on nanoparticle properties but also demonstrates the potential of single-atom surface modification as a means for designing nanoparticle catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)