Article
Chemistry, Organic
Feng Chen, Xiu-Hua Xu, Lingling Chu, Feng-Ling Qing
Summary: A photochemically induced, nickel-catalyzed radical cross-coupling reaction has been developed for the synthesis of alpha-aryl-alpha-trifluoromethyl alcohols. This reaction utilizes a photoinduced charge transfer process between Hantzsch ester and phthalimido trifluoroethanol to generate a radical intermediate for the cross-coupling with aryl bromides. The protocol is mild and operationally simple, without the need for exogenous photocatalysts or stoichiometric metal reductants, and exhibits broad substrate compatibility and excellent functional group tolerance.
Article
Chemistry, Organic
Fang Xiao, Jin-Hong Lin, Fei Hao, Xing Zheng, Yu Guo, Ji-Chang Xiao
Summary: A protocol for visible light mediated C-H trifluoromethylation of unactivated (hetero)arenes under blue LED irradiation has been developed. It enables the rapid construction of a range of CF3-containing (hetero)arenes in moderate to high yields from the readily accessible trifluoromethylsulfonyl-pyridinium salt (TFSP). This protocol is also suitable for nitrogen-containing aromatic heterocycles, which are potentially useful in medicinal chemistry.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Yasunori Toda, Katsumi Tanaka, Riki Matsuda, Tomoyuki Sakamoto, Shiho Katsumi, Masahiro Shimizu, Fuyuki Ito, Hiroyuki Suga
Summary: A phosphonium ylide-based visible light organophotoredox catalyst has been developed and utilized for halohydrin synthesis. Experimental mechanistic studies confirmed an oxidative quenching cycle by the ylide catalyst.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Applied
Kaid C. Harper, En-Xuan Zhang, Zhi-Qing Liu, Timothy Grieme, Timothy B. Towne, Daniel J. Mack, Jeremy Griffin, Song-Yuan Zheng, Ning-Ning Zhang, Srinivas Gangula, Jia-Long Yuan, Robert Miller, Ping-Zhong Huang, James Gage, Moiz Diwan, Yi-Yin Ku
Summary: Despite the increase in academic research on photoredox methods, their application in the pharmaceutical and fine chemical industries has been slow. This report describes the modification of a photoredox trifluoromethylation process for scale-up and the investigation of its mechanism. The insights gained from the mechanistic study were used to design and execute two different reactor systems for commercial-scale photoredox chemistry. The process was successfully scaled up to produce over 500 kg of the desired intermediate, with the implementation of fully continuous manufacturing.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2022)
Article
Chemistry, Organic
Satsuki Shigenaga, Haruko Shibata, Koto Tagami, Tadashi Kanbara, Tomoko Yajima
Summary: The eosin Y-catalyzed hydroperfluoroalkylation of electron-deficient alkenes is a selective and efficient reaction that proceeds smoothly under visible light irradiation. This reaction allows for the use of various perfluoroalkyl bromides and electron-deficient olefins, and all required chemicals are readily available and safe.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Su Chen, Luc Van Meervelt, Erik V. Van der Eycken, Upendra K. Sharma
Summary: A mild visible-light-driven palladium-catalyzed radical tandem dearomatization reaction of indoles with unactivated alkenes is described. This reaction exhibited moderate to good yields and good to excellent diastereoselectivities. Under visible-light irradiation, a photo-excited state of the palladium complex was formed, which enabled the transfer of a single electron to N-(2-bromobenzoyl)indoles, leading to a hybrid palladium radical chemistry. This approach provides efficient and atom-economical access to diverse 2,3-disubstituted indoline derivatives.
Article
Chemistry, Organic
Fuyang Yue, Jianyang Dong, Yuxiu Liu, Qingmin Wang
Summary: The protocol allows for the direct visible-light-mediated alkenylation of alkyl boronic acids at room temperature without an external Lewis base, and proposes a mechanism involving benzenesulfinate activation of alkyl boronic acids. It has been demonstrated to be efficient for functionalizing a broad range of cyclic and acyclic primary and secondary alkyl boronic acids with various alkenyl sulfones.
Article
Chemistry, Multidisciplinary
Lanfeng Wei, Yu Wei, Jinli Zhang, Liang Xu
Summary: This research explores a visible-light-induced oxidative dehydrogenative process using an organoboron compound as the photocatalyst and molecular oxygen as the sole oxidant. This approach successfully accessed an array of N-heterocycles under metal-free mild conditions, in good to excellent yields.
Article
Chemistry, Organic
Bin Sun, Rui Zhu, Xiaohui Zhuang, Xiayue Shi, Panyi Huang, Zhiyang Yan, Chuanming Yu, Can Jin
Summary: This efficient and novel method involves regioselective hydroxydifluoroacetamidation of alkenes with bromodifluoroacetamides through a tandem radical pathway mediated by photoredox catalysis under metal-free conditions. The reaction, using Rhodamine 6G as the photocatalyst, produces a series of alpha,alpha-difluoro-gamma-hydroxyacetamides in moderate to excellent yields, demonstrating the advantages of low-cost photocatalyst, readily available starting materials, synthetic convenience, and wide functional group compatibility.
Article
Chemistry, Multidisciplinary
Kathiravan Murugesan, Karsten Donabauer, Burkhard Konig
Summary: The study demonstrates the use of the commercially available organic dye TPP for the photocatalytic conversion of methylarenes to aryl nitriles, providing a wide range of cyanobenzenes under metal- and cyanide-free conditions. The presented synthetic protocol is applicable for gram-scale reactions and includes detailed mechanistic investigations supporting the proposed catalytic cycle.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Yu-Zhao Wang, Peng-Yu Liang, Hong-Chao Liu, Wu-Jie Lin, Pan-Pan Zhou, Wei Yu
Summary: The annulation reactions of benzoamidyl radicals with alkenes under visible light irradiation using fac-Ir(ppy)(3) as a catalyst and N-aminopyridinium salts as precursors yielded different products depending on the structure of the alkene. Factors influencing the reaction outcome were elucidated by DFT calculations.
Article
Chemistry, Multidisciplinary
Kimihiro Komeyama, Takuya Michiyuki, Yoshikazu Teshima, Itaru Osaka
Summary: The scope of the Giese reaction is expanded using readily available alkyl tosylates as substrates and nucleophilic cobalt(i) catalysts under visible-light irradiation, preferentially with less bulky primary alkyl tosylates. This unique reactivity enables the regio-selective Giese reaction of polyol derivatives.
Article
Chemistry, Organic
Yu-Zhao Wang, Wu-Jie Lin, Hong-Chao Liu, Wei Yu
Summary: This study presents a visible-light-promoted intermolecular radical amidation/cyclization of arylacrylamides using N-aminopyridinium salts as the source of amidyl radicals. The reaction demonstrates a broad scope and good functional group tolerance, enabling the synthesis of a variety of amide-tethered-oxindoles in moderate to good yields.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Applied
Jianlin Chun, Honglin Zhang, Fei Meng, Kang Guo, Shujun Cao, Qin Fang, Jie Li, Yingguang Zhu
Summary: A new synthetic method has been developed for the efficient synthesis of tetrahydrofurans or tetrahydropyrroles containing trifluoromethyl groups through a tandem reaction. This mild and facile protocol allows for the direct access to trifluoromethyl group-bearing compounds from olefins.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Qiang Hu, Wan-Lei Yu, Yong-Chun Luo, Xiu-Qin Hu, Peng-Fei Xu
Summary: Herein, we report an efficient photoinduced radical tandem trifluoromethylation/cyclization reaction for the synthesis of functionalized quinazolinones. The reaction can be carried out under mild conditions without any additional photosensitizer, metal, or extra additives. A series of trifluoromethyl quinazolinones were efficiently prepared with good yields and excellent functional group tolerance, indicating the potential of this method for diverse applications.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
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)
Review
Chemistry, Multidisciplinary
Arthur Desvals, Norbert Hoffmann
Summary: Photocycloadditions of benzene derivatives with alkenes are important in organic synthesis, especially intramolecular reactions. Competition between meta or [2 + 3] photocycloadditions and ortho or [2 + 2] additions is common. The influence of substitution pattern and spin multiplicity on reaction outcomes is discussed. A topological analysis allows for systematic application of [2 + 3] photocycloadditions in total synthesis of natural products, with corresponding syntheses discussed. Recent research has also focused on [2 + 2] photocycloadditions and consecutive rearrangements in organic synthesis, including approaches in asymmetric synthesis.
AUSTRALIAN JOURNAL OF CHEMISTRY
(2023)
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)
Editorial Material
Multidisciplinary Sciences
Huifeng Yue, Chen Zhu, Magnus Rueping
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)
Article
Chemistry, Organic
Mohammed Latrache, Corentin Lefebvre, Manabu Abe, Norbert Hoffmann
Summary: Photochemically induced intramolecular hydrogen atom transfer in oxazolones has been reported. The reaction produces C-C or C-N bond formation. The regioselectivity of the reaction is determined by the zwitterionic structure in the singlet state.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Dan He, Yawen Li, Fuwen Zhao, Yuze Lin
Summary: High trap density in organic solar cells leads to localized charge carriers and reduced carrier lifetime, limiting device efficiency. This feature article summarizes the recent advances of trap suppression by material design and device engineering.
CHEMICAL COMMUNICATIONS
(2024)
Review
Chemistry, Multidisciplinary
Olivier Monfort, Arshitha Madhusudhan, Martin Motola
Summary: This article presents the advantages of coupling photocatalysis and Fenton-based processes for environmental remediation and discusses their synergy. It critically examines the simultaneous triggering of these two processes and provides insights into research approaches. The study aims to enhance understanding of this complex process and highlight the potential integration of new catalysts in current wastewater treatment technology.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Manideepa Dhar, Chittaranjan Mishra, Avijit Das, Uttam Manna
Summary: An approach of 'polymerization of monomers in its aggregated form' has been introduced to tailor the water wettability of fibrous and porous substrates, achieving hydrophobicity to superhydrophobicity transition, as well as patterned wettability. This facile chemical method provides a durable coating with adjustable and patterned wettability for various potential applications.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Saswat Ranjan Bhoi, Chhanda Debnath, Shikha Gandhi
Summary: In this article, a novel catalytic reaction using Pd(0) and Bronsted acid is reported for the synthesis of biologically important imidazolidinone-fused N-heterocycles through redox-neutral intramolecular N-allylation of indoles and pyrroles with alkynes. This atom-economical method is applicable to a wide range of substrates and eliminates the need for leaving groups or oxidizing agents commonly used in traditional allylation reactions.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Longkun Chen, Mingshuai Zhang, Meichen Liu, Zhuoyuan Liu, Yuetong Qiu, Zhilai Zhang, Fuchao Yu, Jiuzhong Huang
Summary: In this study, an efficient Rh(III)-catalyzed selective mono- and dual-C-H bond functionalization/cyclization with iodonium ylide as the sole coupling partner was demonstrated. Fused benzodiazepine skeletons were obtained in excellent yields, providing an improved approach to dual C-H unsymmetrical functionalization.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Alice Kennett, Sven Epple, Gabriella van der Valk, Irene Georgiou, Evelyne Gout, Romain R. Vives, Angela J. Russell
Summary: This study presents the design and synthesis of sulfated disaccharide inhibitors based on IdoA(2S)-GlcNS(6S), which showed potent inhibition of Sulf-2. The results suggest that IdoA(2S)-GlcNS(6S) is the shortest fragment size required for effective inhibition of Sulfs, and a trisulfated disaccharide is identified as the minimal fragment size of heparan sulfate for effective endosulfatase inhibition.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Mauro Garbini, Andrea Brunetti, Riccardo Pedrazzani, Magda Monari, Massimo Marcaccio, Giulio Bertuzzi, Marco Bandini
Summary: The self-adaptability of galvanostatic electrolysis was found to be helpful in a multistage chemo- and diastereoselective electrochemically promoted cyclodimerization of chalcones. Through a series of reductive events, densely functionalized cyclopentanes with five contiguous stereocenters were obtained (25 examples, yields up to 95%, dr values up to >20:1). Further experimental and electrochemical investigations indicated the crucial role of dynamic kinetic resolution of the aldol intermediate in the reaction mechanism.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Dhananjay S. Nipate, Neha Meena, Prakash N. Swami, Krishnan Rangan, Anil Kumar
Summary: In this study, the synthesis of functionalized benzo[a]phenazines and indazolo[2,3-a]quinolines was achieved through Rh(III)-catalyzed oxidative annulation of 2-arylquinoxalines and 2-aryl-2H-indazoles with allyl alcohols. The method showed a wide substrate scope, excellent functional group tolerance, good to high yields of annulated products, and the capability for scaled-up synthesis. A tentative mechanism of the annulation reaction was proposed based on a preliminary mechanistic investigation.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Ruonan Zhang, Abudukadi Tudi, Xia Yang, Xuping Wang, Zhihua Yang, Shujuan Han, Shilie Pan
Summary: A new lead tellurium borate material with a unique fundamental building block [B4O10] was synthesized and found to exhibit high birefringence. The structure-property relationship was discussed using first-principles calculations.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Amresh Kumar Singh, Baishali Thakurta, Anupam Giri, Monalisa Pal
Summary: This study introduces three key concepts for the quick synthesis of large-scale high-quality 2D materials films and their utilization in device fabrication.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Reina Hagiwara, Shun Nishimura, Kosuke Okeyoshi
Summary: A copolymer-conjugated nanocatalytic system has been developed to improve electron transfer and enhance photoinduced H2 generation.
CHEMICAL COMMUNICATIONS
(2024)
