Article
Chemistry, Multidisciplinary
Kevin Blaesing, Rene Labbow, Axel Schulz, Alexander Villinger
Summary: The chemistry of silylated sulfuric acid was studied in detail in order to synthesize the formal autosilylation products, [T3SO4](+) and [TSO4](-). The successful synthesis of [TSO4](-) required the use of a base that forms a weakly coordinating cation upon silylation, while [T3SO4](+) salts could be isolated when a weakly coordinating anion was used as counterion. All silylated compounds were able to be crystallized and structurally characterized.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Engineering, Chemical
I Sanchis, E. Diaz, A. H. Pizarro, J. J. Rodriguez, A. F. Mohedano
Summary: Nitrate pollution of water bodies is a serious global environmental problem, and there is a lack of cost-effective solutions for its removal. Catalytic reduction is an emerging technology that can transform nitrate into harmless nitrogen gas, but it faces challenges in stability and catalyst regeneration.
SEPARATION AND PURIFICATION TECHNOLOGY
(2022)
Article
Chemistry, Inorganic & Nuclear
Martin Ertl, Uwe Monkowius, Kerstin T. Oppelt
Summary: This study investigates the reactivity of a series of Re tricarbonyl complexes with 8-(diphenylphosphanyl)quinoline or 8-(diphenylarsanyl)quinoline as bidendate ligands, comparing them with other complexes. Electrochemical and spectroelectrochemical methods were employed, along with time-resolved spectroscopy, to study the peculiar reactivity of these complexes, including reduction reactions and reactions involving protons.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Subhojit Mondal, Boris Stevanovic, Eric Butler, Jason W. Wang, Michael W. Meanwell
Summary: We propose a mild, electrochemical trihydrodefluorination (e-THDF) method for breaking highly stable C-F bonds in trifluoromethyl arenes to form methyl arene products. This green approach relies on the generation of Lewis acidic silyl cations in situ, which mediate fluoride abstraction. e-THDF shows significantly improved functional group tolerance compared to current methods, and could inspire further development of defluorinative processes.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Zi-Jie Gong, Yemineni S. L. Narayana, Yen-Chun Lin, Wei-Hsiang Huang, Wei-Nien Su, Yi-Pei Li, Masayoshi Higuchi, Wen-Yueh Yu
Summary: In this study, ruthenium-based metallo-supramolecular polymers (Ru-MSPs) were synthesized and used for heterogeneously catalytic transfer hydrogenation of carbonyl compounds. The polymerization process was controlled by adjusting the ligand/metal ratio and synthesis conditions. The coordinatively unsaturated ruthenium atoms were identified as the active sites for carbonyl reduction, and the Ru-MSPs exhibited enhanced activity and reusability compared to monomeric counterparts.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2022)
Article
Chemistry, Physical
Muhammad Mateen, Muhammad Nadeem Akhtar, Ling Gao, Weng-Chon (Max) Cheong, Shanshan Lv, Yan Zhou, Zheng Chen
Summary: Through an emulsion-based molecule-nanoparticle self-assembly strategy, the Ir-1@CeO2 catalyst exhibited exceptional selectivity in the hydrogenation of α, β-unsaturated aldehydes, achieving close to 100% selectivity towards unsaturated alcohols.
Article
Chemistry, Inorganic & Nuclear
Xiao-Hui Wang, Zheng-Min Wang, Qing-Ling Hong, Ze-Nong Zhang, Feng Shi, Dong-Sheng Li, Shu-Ni Li, Yu Chen
Summary: This study successfully synthesized high-quality hollow Cu2O nanocubes, which exhibited high selectivity and activity for electrocatalytic nitrate reduction reaction to ammonia.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Sergio Iglesias-Vazquez, Jose Valecillos, Aingeru Remiro, Javier Bilbao, Ana Guadalupe Gayubo
Summary: The regeneration of NiAl2O4 spinel derived catalysts for ethanol steam reforming is challenging due to irreversible deactivation caused by Ni volatilization and catalyst particle fragmentation. The Al2O3 content in the catalyst influences the irreversible deactivation, which can be controlled by reducing the catalyst at 700-750 degrees C.
Article
Energy & Fuels
Jaehwan Jang, Seongyool Ahn, Sangkyung Na, Jinhee Koo, Heehwan Roh, Gyungmin Choi
Summary: The combustion of fossil fuels in diesel engines causes environmental pollution, especially through NOx emissions. Selective Catalytic Reduction (SCR) systems are considered the most effective technology for reducing emissions in marine diesel applications. However, controlling exhaust gas temperature and preventing catalyst poisoning are crucial for the successful implementation of SCR systems.
Article
Chemistry, Physical
Hongliu Zhang, Xi Chen, Tong Lv, Qian Li, Weidong Liu, Jinhui Feng, Xiangtao Liu, Peiyuan Yao, Qiaqing Wu, Dunming Zhu
Summary: In this study, a mutant M242F/Q245T of the carbonyl reductase from Sporobolomyces salmonicolor was found to enhance its activity toward both methyl 2-phthalimidomethyl-3-oxobutanoate(1a) and isopropanol, enabling the dynamic kinetic asymmetric reduction of 1a to a single stereoisomer of the product by hydrogen transfer from isopropanol. Structural and computational analysis suggested that the synergic effect of 242F and 245T reshaped the substrate entrance tunnel and enzyme active site. This study demonstrated that a carbonyl reductase can be engineered to improve its activity toward bulky ketones and isopropanol, and enable efficient preparation of the target chiral alcohol via substrate-coupled cofactor regeneration.
Article
Chemistry, Multidisciplinary
Weijie Zhu, Fen Yao, Qiongfei Wu, Qiu Jiang, Jinxian Wang, Zhoucheng Wang, Hanfeng Liang
Summary: Researchers have developed a Ru/beta-Co(OH)(2) heterostructure catalyst that shows high activity, selectivity, and stability in electrocatalytic nitrate reduction reaction. The catalyst efficiently converts nitrate pollutants into valuable ammonia products.
ENERGY & ENVIRONMENTAL SCIENCE
(2023)
Article
Multidisciplinary Sciences
Houfu Lv, Le Lin, Xiaomin Zhang, Rongtan Li, Yuefeng Song, Hiroaki Matsumoto, Na Ta, Chaobin Zeng, Qiang Fu, Guoxiong Wang, Xinhe Bao
Summary: By enriching the active Ru, the authors promote the exsolution of RuFe alloy nanoparticles on the surface underneath Sr2Fe1.4Ru0.1Mo0.5O6-δ perovskite, enhancing the current density of CO2 electrolysis. In situ scanning transmission electron microscopy shows the dynamic structure evolution of the perovskite under reducing and oxidizing atmospheres, as well as the facilitated CO2 adsorption at RuFe@Sr2Fe1.4Ru0.1Mo0.5O6-δ interfaces.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Muhammad Mateen, Muhammad Nadeem Akhtar, Ling Gao, Weng-Chon (Max) Cheong, Shanshan Lv, Yan Zhou, Zheng Chen
Summary: Selective hydrogenation of a,β-unsaturated aldehydes can be achieved using atomic engineering of Ir species on CeO2 spheres, resulting in the formation of new Irδ+-O2--Ce3+(O-V) interfaces which promote exceptional selectivity towards unsaturated alcohols.
Article
Chemistry, Physical
Cheng Du, Chenglong Qiu, Zhongying Fang, Ping Li, Yijing Gao, Jianguo Wang, Wei Chen
Summary: A new strategy to enhance the selectivity and activity of nitrogen reduction reaction through self-assembled monolayer has been reported. The strategy inhibits the HER by impeding diffusion of water molecules and promoting adsorption of N2 molecules, thus improving the performance of NRR.
Article
Chemistry, Multidisciplinary
Liu Xu, Shan Xu, Tang Yong Xiang, Lin Wei Chen, Wei Xi Zhong, Ling Zhu, Heng Liu, Li Wu, Wei Dong Li, Yu Tong Wang, Bao Chang Cai, Jun Hong Yao, Rui Chen, Wen Feng Xin, Gang Cao, Zhi Peng Chen
Summary: In this study, a self-assembled chelating peptide hydrogel, named processed pyritum hydrogel (PPH), loaded with an osteogenic metal ion cluster was developed to enhance bone regeneration. PPH was shown to regulate various genes involved in bone regeneration and accelerate the bone healing process. The findings suggest that PPH is a novel, simple, and commercializable bone-regenerating hydrogel with potential clinical use.
JOURNAL OF CONTROLLED RELEASE
(2023)
Article
Chemistry, Multidisciplinary
Zhi-Yuan Zhao, Ming Cui, Elisabeth Irran, Martin Oestreich
Summary: This study successfully achieved highly enantioselective silylation of 3-substituted 2H-azirines using a copper-catalyzed reaction with a silyl boronic ester as a latent silicon nucleophile. The resulting C-silylated, unprotected (N-H) aziridines were obtained in high yields and with excellent enantioselectivities, and they can be further converted into valuable compounds without significant loss of enantiomeric excess.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yi Peng, Martin Oestreich
Summary: Opening the ring of cyclic amines by selectively breaking the carbon-nitrogen bond greatly expands the range of available nitrogen-containing structures. However, methods that can directly open secondary amines are limited. This study presents an efficient reductive ring opening of cyclic amines using PhSiH3 under B(C6F5)(3) catalysis, allowing for the transformation of unstrained cyclic amines into acyclic amines in a simple one-step process. Experimental evidence supports a stepwise mechanism involving silylammonium ions and reductive cleavage of carbon-nitrogen bonds.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Organic
Nektarios Kranidiotis-Hisatomi, Martin Oestreich
Summary: Enantioconvergent transition-metal-catalyzed cross-coupling reactions of racemic a-silyl and a-boryl reagents are important for the synthesis of highly enantioenriched a-chiral silanes and boranes. Palladium, nickel, and copper catalysis are used with a-silyl and a-boryl electrophiles. Numerous chiral ligands have extended the scope of this field. This review summarizes the progress made in this rapidly evolving area.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Organic
Avijit Roy, Haopeng Gao, Hendrik F. T. Klare, Martin Oestreich
Summary: The electrophilic silylium ions were used to investigate the intramolecular Friedel-Crafts-type cyclization of aryl tethered 1,1-difluoroalkenes. The preference for electrophilic silylation of the carbon-carbon double bond over vinylic C(sp(2))-F bonds activation initiates the reaction. Subsequent cyclization and hydrodefluorination of the resulting C(sp(3))-F bonds produce the final product in moderate to good yields. Unlike previous reports, the reaction proceeds with perfluorinated tetraphenylborate counteranion under ambient conditions without the need for a carborate counteranion associated with the silylium ion intermediates.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Organic
Lucie Finck, Sarah Dabrowski, Martin Oestreich
Summary: A denitrogenative palladium-catalyzed C(sp(2))-C(sp(2)) cross coupling reaction of aryl-substituted diazenes capped with a trimethylsilyl group and functionalized aryl bromides is described. The use of a PEPPSITM catalyst in the presence of NaOt-Bu enables the activation of the N-aryl-N'-silyldiazene pronucleophile, leading to the loss of dinitrogen and subsequent coupling with the in-situ-formed aryl nucleophile. This methodology provides access to biaryl compounds with various substituents.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Multidisciplinary
Benedikt Wolff, Zheng-Wang Qu, Stefan Grimme, Martin Oestreich
Summary: This study presents a method for the enantioselective reduction of simple carbenium ions using cyclohexadienes with a hydridic C-H bond at an asymmetrically substituted carbon atom. Chiral cyclohexadienes are used as dihydrogen surrogates for the transfer hydrogenation of alkenes (styrenes). The reaction mechanism involves the initiation by trityl cation and a delicate intermolecular capture of a carbenium-ion intermediate by the chiral hydride source, resulting in good enantiomeric ratios of the reduction products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Min Zhu, Hua-Jie Jiang, Illia Sharanov, Elisabeth Irran, Martin Oestreich
Summary: A desymmetrizing silylation of aromatic diols is achieved by using List's counteranion directed silylation technique for asymmetric silyl ether formation of phenol derivatives. The enantioselective discrimination of achiral 1,1'-biaryl-2,6-diols is enabled by a silylium-ion-like silicon electrophile generated from an allylic silane paired with an imidodiphosphorimidate (IDPi). The enantioselectivity of the desymmetrization is further improved by a downstream kinetic resolution, converting the monosilylated minor enantiomer into the corresponding bissilylated diol.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Benedikt Wolff, Martin Oestreich
Summary: This Review summarizes the approaches taken to achieve the stereoselective addition of nucleophiles to these fleeting intermediates, including recent advances where non-covalent interactions and chiral counterions are employed to discriminate either side of a trigonal-planar carbenium ion bearing three different substituents.
ISRAEL JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Organic
Honghua Zuo, Hendrik F. T. Klare, Martin Oestreich
Summary: A catalytic silylium-ion-promoted intramolecular alkyne carbosilylation reaction is reported, involving electrophilic activation of the C-C triple bond by a silylium ion and maintenance of the catalytic cycle through protodesilylation of an allylsilane reagent. The reaction exhibits exclusive 7-endo-dig selectivity and results in fully substituted vinylsilane derivatives of silylated benzocycloheptenes. Control experiments demonstrate that the catalytically active silylium ion can be regenerated by protodesilylation of the vinylsilane product.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Daniel Broesamlen, Martin Oestreich
Summary: A newly developed hept-4-yl-substituted Pybox ligand enables a nickel-catalyzed enantio- and regioconvergent alkylation of regioisomeric mixtures of racemic germylated allylic electrophiles with alkyl nucleophiles, yielding various chiral gamma-germyl alpha-alkyl allylic building blocks with excellent yields and enantioselectivities. The regioconvergence is attributed to the steering effect of the bulky germyl group. The resulting vinyl germanes can be easily halodegermylated without racemization of the allylic stereocenter, providing synthetically valuable gamma-stereogenic vinyl halides.
Article
Chemistry, Organic
Daniel Bro''samlen, Martin Oestreich
Summary: A Ni-H-catalyzed hydroalkylation of vinylsilanes and -germanes as well as allylsilanes with unactivated alkyl iodides is described. In contrast to reactions with styrene or vinyl boronate esters, the addition across the C-C double bond exhibits anti-Markovnikov selectivity, yielding the linear regioisomer. Mechanistic control experiments confirm a radical mechanism, and a competition experiment demonstrates the chemoselectivity favoring the vinyl group over the allyl group.
Article
Chemistry, Organic
Peng-Wei Long, Tao He, Hendrik F. T. Klare, Martin Oestreich
Summary: This Account summarizes the fascinating chemistry of cyclopropyl-stabilized silylium ions, which can be readily obtained from vinyl-cyclopropanes (VCPs). Depending on the nucleophilic partner, these reactive intermediates undergo direct ring opening or ring expansion, leading to the formation of nonclassical alkene-stabilized silylium ions. The latter can also be obtained by gold and proton electrophiles from silicon compounds containing unsaturated C-C bonds. These reaction cascades can be terminated by the formation of C-H or C-C as well as Si-O bonds, revealing the versatility of these complex reactions.
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.
Article
Chemistry, Multidisciplinary
Yuanjiu Xiao, Lei Tang, Tong-Tong Xu, Jiang-Yi-Hui Sheng, Zhongyan Zhou, Lei Yue, Guoqiang Wang, Martin Oestreich, Jian-Jun Feng
Summary: A boron Lewis acid-catalyzed intermolecular carboacyloxylation of ynamides with esters is reported, which provides a direct and efficient way to access fully substituted acyclic enol esters. The reaction shows high regio- and Z/E selectivity and is compatible with readily available allylic carbonates. This strategy allows the construction of acyclic beta,beta-disubstituted enol carbonates of amides and can be applied to the synthesis of enantioenriched alpha-quaternary amides.
Review
Chemistry, Organic
Lucie Finck, Martin Oestreich
Summary: This perspective provides an overview of the underexplored chemistry of diazenes and highlights their potential in synthetic transformations. The stability and reactivity of diazenes have been enhanced by using silicon protection. The generation of aryl, diazenyl, and alkyl anionic intermediates under catalytic conditions opens up new synthetic approaches as alternatives to existing methodologies.
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)
