Article
Chemistry, Organic
Katherine Townsend, Malcolm P. Huestis, John C. Tellis
Summary: A method for the cross-coupling of S-aryl and S-alkyl potassium thiomethyltrifluoroborates with aryl and heteroaryl bromides is reported using photoredox/nickel dual catalysis. The reaction proceeds under mild conditions, providing benzylthioether products in moderate to good yields with good functional group tolerance. Additionally, a practical and improved synthesis of potassium thiomethyltrifluoroborates is described, offering access to previously undescribed reagents.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Applied
Rongkang Wang, Fangming Chen, Lvqi Jiang, Wenbin Yi
Summary: An efficient electrochemical synthesis method has been developed for the production of various unsymmetrical thioethers and arylboronates. This approach utilizes stable arylazo sulfones as radical precursors for carbon-heteroatom bond formation under electrochemical conditions, and shows scalability for gram-scale reactions. The protocol avoids the use of stoichiometric oxidants, metal catalysts, activating agents, and added bases, while also demonstrating favorable functional group tolerance.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Applied
Yu Gao, Sara Sparascio, Lorenzo Di Terlizzi, Massimo Serra, Guanglu Yue, Yaru Lu, Maurizio Fagnoni, Xia Zhao, Stefano Protti
Summary: Two visible-light mediated protocols for the synthesis of aryl thiocyanates and aryl selenocyanates from arylazo sulfones are presented. The reactions make use of the unique photoreactivity and redox activity of the substrates, and exhibit high yields and wide scope.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Long Yin Lam, Cong Ma
Summary: A Chan-Lam-type C-S coupling reaction using sodium aryl sulfinates has been developed to provide diaryl thioethers in high yields with the presence of a copper catalyst and potassium sulfite. The mechanistic study revealed that potassium sulfite was involved in the deoxygenation of sulfinates through a radical process.
Article
Chemistry, Organic
Xinmiao Huang, Ling Tang, Zhiyong Song, Shuangshuang Jiang, Xianmao Liu, Ming Ma, Bo Chen, Yuanhong Ma
Summary: A nickel catalysis system has been developed for the desulfonylative C(sp(2))-C(sp(2)) reductive cross-coupling reactions of aryl sulfone derivatives with aryl bromides to form diverse biaryl compounds. The isolated and confirmed Ar-Ni(II)-SO(2)CF3 complex with a phosphine ligand through oxidative addition of aryl sulfone to Ni(0) species provides solid evidence for understanding the C(Ar)-SO2 bond activation and reaction mechanism.
Article
Chemistry, Applied
Tien Tan Bui, Van Hieu Tran, Hee-Kwon Kim
Summary: This study presents a visible-light-mediated synthesis of sulfonyl fluorides from arylazo sulfones using K2S2O5 and NFSI as reagents, achieving high yields of the products at room temperature. This protocol provides a useful synthetic approach to sulfonyl fluoride structures.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Ankun Li, Yuxuan Li, Junjie Liu, Jingqi Chen, Kui Lu, Di Qiu, Maurizio Fagnoni, Stefano Protti, Xia Zhao
Summary: This protocol for the synthesis of aryl trifluoromethyl thioethers under visible-light-driven conditions does not require the use of photocatalysts or metal catalysts. It utilizes the unique properties of arylazo sulfones and S-trifluoromethyl arylsulfonothioates as precursors, making the procedure easy to handle.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Xin-Qian Liu, Yang Guo, Wen-Qin Yu, Biquan Xiong, Peng-Fei Huang, Ke-Wen Tang, Yu Liu
Summary: This article describes a visible-light-induced three-component reaction of 2-arylindoles/benzimidazoles, Hantzsch esters, and sodium pyrosulfite for the synthesis of alkylsulfonatedisoquinolinones. Hantzsch esters and Na2S2O5 act as alkyl radical precursors and SO2 surrogate, respectively. This method exhibits good functional group tolerance and substrate applicability under mild conditions.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Chrysoula Mikra, Achilleas Mitrakas, Virginia Ghizzani, Katerina R. R. Katsani, Maria Koffa, Michael Koukourakis, George Psomas, Stefano Protti, Maurizio Fagnoni, Konstantina C. C. Fylaktakidou
Summary: Arylazo sulfones that undergo N-S bond cleavage upon light exposure were synthesized, and their activity towards DNA in the dark and upon irradiation was investigated. Molecular docking calculations revealed the mechanism of DNA interaction, and UV-A irradiation significantly enhanced DNA damage. In vitro experiments showed that these compounds slightly increased cell death upon irradiation. These findings suggest that these compounds may be used for the development of phototoxic pharmaceuticals.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Organic
Dmitry I. Bugaenko, Alexey A. Volkov, Alexander V. Karchava
Summary: Most existing methods for alkyl arylthioether synthesis rely on using mercaptans as starting materials, which has practical limitations. A thiol-free method for the synthesis of these valuable compounds is proposed, utilizing reactions between diaryliodonium salts and xanthate salts, derived from corresponding alcohols and CS(2), under the developed conditions. The protocol showcases high functional group tolerance and can be used for late-stage C-H functionalization and introduction of a CD3S group.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
E. William Webb, Kevin Cheng, Jay S. Wright, Jocelyn Cha, Xia Shao, Melanie S. Sanford, Peter J. H. Scott
Summary: Radiocyanation is an attractive and complementary strategy for incorporating carbon-11 into radiotracer targets. This approach utilizes a Cu-11CN complex to capture aryl radical intermediates, enabling rapid and mild radiocyanation. Examples include the reaction of CuI with aryldiazonium salt and visible-light photocatalysis of aryl iodides, both followed by coupling with Cu-11CN to access challenging radiocyanated products.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Ding-Xing Wang, Hui Wang, Yao Xu, Chi Zhang, Chao Feng
Summary: A photoredox catalysed 1,3-oxylallylation of aryl cyclopropanes was achieved by reacting with carboxylic acids and allyl sulfones. The redox-neutral reaction exhibited high regioselectivity under mild conditions and showed good functional group compatibility. The protocol also demonstrated simple operation and successful application in the late-stage functionalization of natural product and pharmaceutical molecule related carboxylic acids.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Yulei Zhao, Shuai Li, Yuhang Fan, Jun Cao, Xiaotong Dong, Ruiqing Wang, Laijin Tian
Summary: An unprecedented C-sp3-H imination reaction using arylazo sulfones as the readily accessible and stable N source is reported. The synthetic virtues of this reaction include mild conditions, simple operation, good air compatibility, and functional group tolerance, as well as suitability for gram-scale reaction. The resulting imines can be further converted to α-amino acids. The presented results shed light on the unusual usage of arylazo sulfones and will inspire novel experimental design by using arylazo sulfones as the N source.
Article
Chemistry, Applied
Fernando Herrera, Pablo Esteban, Amparo Luna, Pedro Almendros
Summary: The synergy between metal catalysis and radical chemistry has enabled researchers to overcome previous limitations in reactions between allenols and sulfonylating reagents, leading to successful copper-catalyzed cascade cycloetherification/sulfonylation for the controlled preparation of specific products.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Kosho Makino, Kumi Tozawa, Yuki Tanaka, Akiko Inagaki, Hidetsugu Tabata, Tetsuta Oshitari, Hideaki Natsugari, Hideyo Takahashi
Summary: The study revealed that the photoracemization reaction of chiral alkyl aryl sulfoxides is extremely fast and influenced by various substitution patterns. However, chiral sulfoxides with easily oxidizable functional groups are not suitable for this photo-isomerization.
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
Multidisciplinary Sciences
Long Huang, Marcin Szewczyk, Rajesh Kancherla, Bholanath Maity, Chen Zhu, Luigi Cavallo, Magnus Rueping
Summary: In this study, stereodivergent allylic C(sp(3))-H bond arylations were successfully developed through a systematic investigation of the direction and degree of stereoselectivity in the cross-coupling process. Unlike the typical photosensitized geometrical isomerization of alkenes, the catalytic reaction demonstrated the feasibility of switching the C-C double bond stereoselectivity through ligand control and steric and electronic effects.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Sharath Kandambeth, Vinayak S. Kale, Dong Fan, Jeremy A. A. Bau, Prashant M. M. Bhatt, Sheng Zhou, Aleksander Shkurenko, Magnus Rueping, Guillaume Maurin, Osama Shekhah, Mohamed Eddaoudi
Summary: This work reports an innovative strategy for the synthesis of chemically robust metal-organic frameworks (MOFs) and their application as catalysts for the electrocatalytic oxygen evolution reaction (OER). The study demonstrates that bimetallic MOF systems with regulated metal ratios exhibit excellent catalytic activity and structural stability for OER.
ADVANCED ENERGY 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.
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)
Review
Chemistry, Multidisciplinary
Jingchang Zhang, Magnus Rueping
Summary: In recent years, the combination of photocatalytic hydrogen atom transfer (HAT) and transition metal catalysis has become an important strategy for the synthesis of C(sp(3))-carbon and C(sp(3))-hetero bonds. This approach has been widely used in organic synthesis, leading to new transformations. This review summarizes the recent advances in sp(3) C-H functionalizations through photocatalytic HAT followed by transition metal catalysis, focusing on the diverse strategies, synthetic applications, and detailed mechanisms involved in these reactions. The understanding of these mechanisms is crucial for the rational design of new catalysts and reaction conditions to improve the efficiency of these transformations. We hope that this review will serve as a valuable resource for researchers in the field of metallaphotoredox catalysis and inspire further development in green chemistry, drug synthesis, material science, and other related fields.
CHEMICAL SOCIETY REVIEWS
(2023)
