Article
Chemistry, Multidisciplinary
Nurbey Gulia, Jaroslaw Fornalski, Adrianna Gumienna, Malgorzata Ambroziak, Slawomir Szafert
Summary: This study reports a method of palladium-catalyzed C-H arylation assisted with a 3,4,4-trimethylpyrazol-5-on directing group, which selectively provides mono- and di-ortho-arylated products. The steric hindrance between the directing group and the already introduced aryl substituent enables control of mono- vs. diarylation selectivity by the reaction temperature. A series of monosubstituted and disubstituted derivatives were obtained in good yields. In addition, a one-pot procedure for unsymmetrical double-arylation to give corresponding products was developed, and the synthesis and X-ray study of intermediate palladium metallacycles were conducted. The decarboxylative cleavage of the pyrazolone directing group under mild conditions gave synthetically useful hydrazones. Overall, this solution provides an alternative synthetic pathway for ortho arylated derivatives of arylhydrazines.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Review
Chemistry, Multidisciplinary
Tasneem Elkoush, Natasha D. Reich, Michael G. Campbell
Summary: In the past two decades, there has been a significant increase in the number of synthetically useful transformations catalyzed by silver, with dinuclear silver species commonly emerging as a key feature in these reactions. Understanding the role of dinuclear silver complexes in homogeneous catalysis can aid in the development of improved design principles for silver catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Acoustics
Ingrid V. Machado, Jhonathan R. N. dos Santos, Marcelo A. P. Januario, Arlene G. Correa
Summary: By utilizing ultrasound-assisted multicomponent reactions under heterogeneous catalysis, it is possible to efficiently synthesize biologically active organic compounds with reduced costs and energy consumption.
ULTRASONICS SONOCHEMISTRY
(2021)
Article
Chemistry, Physical
Froze Jameel, Matthias Stein
Summary: In the global effort to combat climate change, the design and development of new procedures for complex chemical multi-step reactions play a crucial role in the transformation of the chemical industry. Solvent effects on thermodynamics and kinetics are important considerations, with various roles including promoting intermediate formation but also compromising overall pathways. Solvent coordination is critical for the activity of reducing catalysts, impacting regioselectivity and reaction rates in complex multi-step reactions.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Applied
Philipp M. Stein, Matthias Rudolph, A. Stephen K. Hashmi
Summary: Water has an impact on the rate constant of gold-catalyzed reactions, not only showing tolerance but also potentially promoting reactions in some cases. Kinetic data demonstrates that the addition of water in gold catalysis can lead to better results.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Inorganic & Nuclear
Hong Tang, Ming Yang, Xin Li, Mei-Li Zhou, Yan-Sai Bao, Xin-Yu Cui, Kun Zhao, Yu-Yang Zhang, Zheng-Bo Han
Summary: The study accelerated heterogeneous homocoupling reactions of phenylboronic acids via a tandem route utilizing a bifunctional heterogeneous catalyst of metal organic frameworks encapsulated with palladium nanoparticles. This strategy successfully formed symmetric C-C bonds between benzene rings, demonstrating advantages such as high efficiency, easy separation, good recyclability, and no addition of toxic substances.
INORGANIC CHEMISTRY COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Dominik Birnthaler, Rok Narobe, Eliseo Lopez-Berguno, Christoph Haag, Burkhard Koenig
Summary: Ligand-to-metal charge transfer (LMCT) photo-catalysis enables the activation and utilization of halides and other heteroatoms in metal complexes. The application of bismuth LMCT in organic radical coupling reactions has been expanded, generating chlorine and carboxyl radicals in net-oxidative and redox-neutral photochemical reactions. The study reveals BiCl4- and BiCl52- as the catalytically active bismuth species under 385 nm irradiation, providing insight into the reactivity of the highly reactive bismuth(II) catalyst fragment through cyclic voltammetry and UV-vis studies.
Article
Chemistry, Multidisciplinary
Max J. Hulsey, Geng Sun, Philippe Sautet, Ning Yan
Summary: The article discusses the use of electrospray ionization mass spectrometry (ESI-MS) to study single-atom catalysts supported on polyoxometalates in catalytic reactions, revealing the composition of active sites and their evolution in the catalytic cycle.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Applied
Seoung-Mi Choi, Ju Hyun Kim
Summary: This review summarizes the progress made in the synthesis of 2H-pyrroles since 2000, including methods such as dearomatization of 1H-pyrrole, oxidation of pyrrolines or pyrrolidines, ring construction via catalytic cycloaddition, and rearrangement of 3H-pyrroles.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Alexander Reichle, Magdalena Koch, Hannes Sterzel, Lea-Joy Grosskopf, Johannes Floss, Julia Rehbein, Oliver Reiser
Summary: The visible light-mediated copper-catalyzed vicinal difunctionalization of olefins utilizing bromonitroalkanes as ATRA reagents is reported. This method offers high yields, fast reaction times, and environmentally benign reaction conditions with a wide scope, allowing rapid functionalization of activated and unactivated olefins. Additionally, it demonstrates the late-stage functionalization of biologically active molecules and the upscaling to gram quantities, providing possibilities for further transformations such as the preparation of nitro- and aminocyclopropanes. Moreover, this study highlights the unique role of copper in photoredox catalysis by stabilizing and interacting with radical intermediates in its coordination sphere, as revealed by EPR studies that show its superior performance compared to iridium-based photocatalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Zhenhua Zhang, Julius B. Stueckrath, Stefan Grimme, Andreas Gansaeuer
Summary: Cp2Ti(TFA) is a versatile catalyst for the [2+2] cycloaddition of bisenones through inner-sphere electron transfer, with a unique 5-exo step as the rate-determining step followed by a favorable 4-exo cyclization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Julia C. Reisenbauer, Benjamin N. Bhawal, Nicola Jelmini, Bill Morandi
Summary: This article reports a method for hydrocyanation reactions of alkenes and alkynes using commercially available aliphatic nitriles as a substitute for toxic hydrogen cyanide (HCN). The reaction employs a catalytic amount of inexpensive and stable NiCl2 along with a cocatalyst. The scalability and robustness of this method have been demonstrated.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2022)
Article
Chemistry, Applied
Maxime Denis, Samuel Blais, Sylvain Canesi
Summary: A stereoselective synthesis of isolycoricidine, a natural product belonging to the Amaryllidaceae alkaloids family, was achieved. The study also conducted a synthetic investigation on the main core of lycoricidine, resulting in the formation of analogues and a diastereomer of dihydrolycoricidine. The research utilized various strategies including oxidative phenol dearomatization, stereoselective Heck process, selective dihydroxylation, stereoselective reductions, and oxidative retro-Michael procedure as an amine-deprotecting group strategy. In addition, the study highlighted the usefulness of hypervalent iodines in total synthesis of natural products.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Wen-Xuan Cao, Lei Zhu, Yiyi He, Run Wang, Ming Liu, Qin Ouyang, Qing Xiao
Summary: The first aryne insertions into the carbon-iodine bond of heteroaryl iodides have been achieved. This novel reaction provides an efficient pathway for the synthesis of valuable building blocks 2-iodoheterobiaryls with excellent regioselectivity by reacting heteroaryl iodides and o-silylaryl triflates. The copper(I) catalyst, which contains a N-heterocyclic carbene (NHC) ligand, is essential for the reaction. Control reactions and DFT calculations suggest that the coordination of copper, acting as a Lewis acid, with nitrogen atoms of heteroaryl iodides mediates the aryne insertions into heteroaryl carbon-iodine bonds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Xiong Xiao, Zhi-Xiang Yu
Summary: The research presents a highly enantioselective intramolecular [3+2] cycloaddition of yne-alkylidenecyclopropanes using a cheap Co catalyst and commercially available chiral ligand, achieving up to 92% enantiomeric excess. Experimental evidence suggests cationic cobalt(I) species as the catalytic species, with a mechanism differing from previous [3+2] reactions of ACPs.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
You-Jie Yu, Michael Schaefer, Constantin G. Daniliuc, Ryan Gilmour
Summary: A catalysis-based regioselective method for the synthesis of compact, highly functionalized products from trifluoromethyl substituted 1,3-dienes has been developed. The new method allows E,Z-mixed dienes to be converted to a single E-alkene isomer and utilizes an inexpensive and convenient I(I)/I(III) catalysis platform. This method enables the synthesis of delta-fluoro-alcohol and amine derivatives in a single operation, and is compatible with various nucleophiles.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Xiaoming Jie, Chaohuang Chen, Constantin G. Daniliuc, Gerald Kehr, Gerhard Erker
Summary: The hydroboration of styrene or vinylcyclohexane with the IMes(C6F5)BH+ cation followed by deprotonation provides a convenient synthetic route to boraalkenes [B]=CHCH2R. The in-situ generated IMes(SCN)BH+ system reacts similarly with 1,1-diphenylethene, resulting in the formation of isothiocyanato-substituted boraalkene. The boraalkenes participate in [2+2] cycloaddition reactions with heterocumulenes, yielding respective four-membered heterocycles. The addition of borane HB(C6F5)(2) to [B]=CHCH2R+CO2 cycloadducts leads to cleavage of the central B-C sigma-bond.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jessica Neufeld, Constantin. G. G. Daniliuc, Ryan Gilmour
Summary: This study presents a regioselective fluorocyclisation of beta,gamma-unsaturated oximes through I(I)/I(III) catalysis, using p-iodotoluene as a cost-effective catalyst, Selectfluor((R)) as the oxidant, and an amine.HF complex as the fluoride and Bronsted acid source. The transformation produces 5-fluoromethylated isoxazolines, with a range of aliphatic and aromatic systems yielding up to 56%.
HELVETICA CHIMICA ACTA
(2023)
Article
Chemistry, Medicinal
Tobias Schierling, Beatrice Tosi, Clara Eisenhardt, Sophie Reining, Constantin G. Daniliuc, Christoph Brenker, Timo Struenker, Bernhard Wuensch
Summary: This article introduces a new and more effective inhibitor for studying sperm swimming behavior. The inhibitor is structurally simpler and easier to synthesize compared to existing inhibitors, and shows even better potency. It is envisioned to be widely used in future studies on the physiology of CatSper in sperm.
ACS PHARMACOLOGY & TRANSLATIONAL SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Yujie Liang, Fritz Paulus, Constantin G. Daniliuc, Frank Glorius
Summary: We report a BF3-catalyzed [2 + 2] cycloaddition reaction between aldehydes and bicyclo[1.1.0]butanes (BCBs) to access polysubstituted 2-oxabicyclo[2.1.1]hexanes. A new BCB containing an acyl pyrazole group was discovered, which not only facilitates the reactions but also allows for diverse downstream transformations. Additionally, aryl and vinyl epoxides can be used as substrates that undergo cycloaddition with BCBs after in situ rearrangement to aldehydes. These results will promote the exploration of complex sp(3)-rich bicyclic frameworks and BCB-based cycloaddition chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jannik Reimler, Xiao-Ye Yu, Nico Spreckelmeyer, Constantin G. Daniliuc, Armido Studer
Summary: The Friedel-Crafts acylation reaction has been a valuable and versatile reaction, but a new radical approach for the acylation of arenes and heteroarenes is presented in this study. By using cooperative photoredox/NHC radical catalysis, C-H acylation is achieved with regiodivergent outcomes. Aroyl fluorides act as the acylation reagents in both the ionic and radical processes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Max Wienhold, Byeongseok Kweon, Calum McLaughlin, Matthias Schmitz, Till J. B. Zaehringer, Constantin G. Daniliuc, Christoph Kerzig, Ryan Gilmour
Summary: Amide groups are widely present in the chemical space continuum, and their structural and pharmacological importance as well as hydrolytic vulnerabilities drive the development of bioisosteres. Alkenyl fluorides have a long history as effective mimics, but emulating peptide bond isomerization with fluoro-alkene surrogates is challenging. This study presents a design of an ambiphilic linchpin that enables isomerization process, providing geometrically-programmable building blocks for small molecule amide and polyene isostere discovery.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Roman Kleinmans, Subhabrata Dutta, Kristers Ozols, Huiling Shao, Felix Schafer, Rebecca E. Thielemann, Hok Tsun Chan, Constantin G. Daniliuc, Kendall N. Houk, Frank Glorius
Summary: The ortho-selective intermolecular photocycloaddition of bicyclic aza-arenes is reported, utilizing a strain-release approach. This reaction enables the construction of C-(sp(3))-rich bicyclo-[2.1.1]-hexanes directly connected to N-heteroarenes. Photophysical experiments and DFT calculations reveal the mechanism of this selective intermolecular photocycloaddition.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Biochemistry & Molecular Biology
Gina Vasile Scaeteanu, Constantin G. Daniliuc, Rodica Olar, Mihaela Badea
Summary: A complex [Zn(bpy)(acr)(2)]center dot H2O was converted into a coordination polymer [Zn(bpy)(acr)(HCOO)](n) in a DMF medium. The polymer was fully characterized through crystallographic analysis, IR, and thermogravimetric analysis. The obtained complex, with its unique composition and structure, is of current interest and rarely reported in the literature.
Article
Chemistry, Multidisciplinary
Benedikt Sieland, Marcel Stahn, Roland Schoch, Constantin Daniliuc, Sebastian Spicher, Stefan Grimme, Andreas Hansen, Jan Paradies
Summary: An isostructural series of boron/phosphorus Lewis pairs were investigated systematically. The association constants of the Lewis pairs were determined and thermodynamic parameters were extracted at different temperatures. The stabilization of the Lewis adduct increased with the size of the dispersion energy donor groups, despite the donor and acceptor properties of the Lewis pairs remaining largely unchanged. This data was used to challenge state-of-the-art quantum chemical methods and resulted in an enhanced workflow for accurately determining the thermochemical properties of weakly bound Lewis pairs.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Fabian Hoeglsperger, Fayaz Ali Larik, Changzhuang Bai, Maximilian D. Seyfried, Constantin Daniliuc, Henning Klaasen, Pall Thordarson, Jonathon E. Beves, Bart Jan Ravoo
Summary: In this study, water-soluble arylazoisoxazole photoswitches were introduced. The photostationary states and reversible photoisomerization between E- and Z-isomers were observed, indicating their potential for photoresponsive host-guest chemistry in water. Furthermore, hydrogel properties can be manipulated reversibly with light. Overall, arylazoisoxazoles have great potential as molecular photoswitches in aqueous media.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Zi-Xuan Wang, Keith Livingstone, Carla Huempel, Constantin G. Daniliuc, Christian Mueck-Lichtenfeld, Ryan Gilmour
Summary: Fluorinated small molecules are commonly used in the field of functional small molecules. Researchers have developed creative approaches to access these important materials by utilizing iodine(I)/iodine(III) catalysis to convert abundant alkene substrates into high-value (di)fluorinated products. They also discovered that enynes can be used as proxies for styrenes, simplifying the process and enabling the generation of highly versatile homopropargylic difluorides.
Article
Chemistry, Organic
Shyam Kumar Banjare, Dirk Leifert, Frauke Weidlich, Constantin G. Daniliuc, Fatmah A. Alasmary, Armido Studer
Summary: An oxidative radical cascade addition cyclization approach using eco-friendly iron catalysis and inexpensive tert-butylhydroperoxide (TBHP) as the oxidant has been reported for the synthesis of quinoline-based p-extended polyheterocyclic compounds. This method utilizes readily available ortho-alkynylated aromatic aldehydes as radical precursors and aryl isonitriles as radical acceptors. By applying this approach, quinolines that are p-conjugated with an additional heteroarene moiety can be prepared in a single sequence using indole and thiophene-based carbaldehydes.
Article
Chemistry, Multidisciplinary
Timo Stuenkel, Kathrin Siebold, Daichi Okumatsu, Kazuki Murata, Louise Ruyet, Constantin G. Daniliuc, Ryan Gilmour
Summary: The regio- and enantio-selective dearomatization of phenols has been achieved using I(i)/I(iii) catalysis enabled fluorination. The reaction is highly selective and efficient, offering great potential in the field of hydroxylation chemistry.
Article
Chemistry, Organic
Tobias Winge, Dirk Schepmann, Judith Schmidt, Constantin Daniliuc, Ernst-Ulrich Wuerthwein, Bernhard Wuensch
Summary: Spirocyclic scaffolds are important in drug discovery as they enhance specific interactions with protein binding sites. This study synthesized a series of spirocyclic compounds and found that one of them exhibited favorable pharmacological and physicochemical properties.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)