Article
Chemistry, Multidisciplinary
Karel Skoch, Constantin G. Daniliuc, Gerald Kehr, Gerhard Erker
Summary: The compound undergoes a rare reaction with a borane to form a unique unsaturated compound, capable of reducing carbon monoxide and reacting with nitriles to produce a boron-containing heterocycle derivative.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Fuyu Xie, Jianghua He, Yuetao Zhang
Summary: This article presents a strategy for generating Frustrated radical pairs (FRP) using a Lewis acid and a Lewis base. The FRP can efficiently initiate atom-transfer radical addition (ATRA) reactions, resulting in high regioselectivity and high yields of fluoroalkylated compounds.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Inorganic & Nuclear
Hannah J. J. Dokken, Brandon L. L. Frenette, Michael J. J. Ferguson, Eric Rivard
Summary: We report the synthesis and reactivity of a geminal-linked fluorene-derived frustrated Lewis pair (FLP), (Pr2P)-Pr-i(C13H8)BCy2 (1). Compound 1 displays anomalous behavior towards small molecules, acting as a masked FLP. This behavior is attributed to significant polarization of the B-C(fluorene) bond in 1, as determined by density functional theory (DFT) computations. We show the exploitation of this B-C bond polarity through reactions with PhPCl2, H3N center dot BH3, and (PrNH2)-Pr-i, leading to P-Cl and N-H bond activation, respectively.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Brandon L. L. Frenette, Jonathan Trach, Michael J. J. Ferguson, Eric Rivard
Summary: We report the stabilization of phosphinidenes (PR) by an intramolecular frustrated Lewis pair (FLP) chelate. Our new adducts, including PH accessed through thermolysis of coordinated HPCO, act as a starting point for other phosphorus-containing compounds. These adducts participate in thermal- or light-induced phosphinidene elimination, transfer P-2 units to an organic substrate, and yield the semiconductor InP at only 110 degrees C from solution.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Swapan Sinha, Santanab Giri
Summary: In this study, a new frustrated Lewis pair (FLP) was designed to activate the H2O molecule. The activation mechanism and charge transfer processes were thoroughly analyzed and revealed through calculations and analysis.
CHEMICAL PHYSICS LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Lucas Kistner, Dario Kowatsch, Andreas Marz, Elisabeth Kaifer, Hans-Joerg Himmel
Summary: The chemistry of dicationic diboranes with direct B-B bonding is largely unexplored. In this work, stable unsymmetric dicationic diboranes were synthesized by reacting an electron-rich ditriflato-diborane with phosphino-pyridines, forming B-N and B-P bonds. The formation of one of the compounds required several days at ambient conditions, creating an intermediate for frustrated Lewis pair (FLP)-like chemistry.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Wenhao Yu, Yanyun Zhang, Yingnan Qin, Dan Zhang, Kang Liu, G. A. Bagliuk, Jianping Lai, Lei Wang
Summary: This study presents a method to construct catalysts with regulable acidity and basicity by utilizing the Mott-Schottky effect on an intermetallic alloy. The developed fct-PtCo@NC catalyst with high-density frustrated Lewis pair (FLP) sites shows outstanding performance in the hydrogen evolution reaction. The synergistic effect of FLP-acid sites and FLP-base sites significantly reduces the energy barrier between water adsorption and decomposition, resulting in faster reaction kinetics.
ADVANCED ENERGY MATERIALS
(2023)
Review
Chemistry, Multidisciplinary
Pallavi Sarkar, Shubhajit Das, Swapan K. Pati
Summary: This article summarizes the progress in the study of non-boron Lewis acids since 2015, which are an important component of Frustrated Lewis pairs.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Thaddaeus Thorwart, Deborah Hartmann, Lutz Greb
Summary: In this study, a novel Lewis acid was reported and successfully applied in dihydrogen activation, which has been elusive for non-planar Lewis acid. This research result is important for understanding the mechanism of FLP reactions.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Ryo Oshimizu, Naoki Ando, Shigehiro Yamaguchi
Summary: In this study, the weak interaction between olefin-borane pi-complexes and frustrated Lewis pairs (FLP) was utilized to modulate the electronic properties of boron-based pi-electron materials. By adding Lewis bases, FLP-type addition reactions occurred, leading to significant changes in the absorption and emission properties of the fluorophores. These findings offer a design strategy for stimuli-responsive emissive boron-based materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Kinga Kaniewska-Laskowska, Marcin Czapla, Jaroslaw Chojnacki, Rafal Grubba
Summary: The concept of nonmetallic frustrated cations has been applied in the activation of small molecules. In situ generated ambiphilic phosphinoborinium cation can activate phenyl isocyanate, diisopropylcarbodiimide, and acetonitrile under very mild conditions without any catalyst, resulting in single-, double-, or mixed-activation products. Furthermore, the mechanisms of these reactions were elucidated using density functional theory calculations.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Karel Skoch, Constantin G. Daniliuc, Gerald Kehr, Sebastian Ehlert, Marcel Muller, Stefan Grimme, Gerhard Erker
Summary: The attachment of P-stereogenic mesityl(alkynyl)phosphanyl groups at the 4- and 5-positions of a 9,9-dimethylxanthene framework leads to mixtures of rac- and meso-bisphosphanyl diastereoisomers, which slowly epimerize in thermally induced reactions. Further reactions with Piers' borane resulted in alkylidene-bridged geminal bisphosphane/borane-frustrated Lewis pair systems.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Wei Chen, Jingfeng Han, Yingxu Wei, Anmin Zheng
Summary: The frustrated Lewis pair (FLP) concept has been successfully applied to heterogeneous catalysis by using a supramolecular system involving deprotonated zeolite framework oxygens and confined carbocations in methanol-to-olefin (MTO) reactions. This FLP showed the capability of H-2 heterolysis and alkane dehydrogenation, which was confirmed by catalytic experiments using GC-MS inside FLP-containing chabazite zeolites.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Swapan Sinha, Santanab Giri, Arindam Chakraborty
Summary: The possible existence of nonagermanide deltahedral Zintl ion (Ge-9(4-)) as a nine-folded Lewis base is investigated from first principles calculations. It is observed that all nine centres, Ge-9(4-), can make an adduct with Lewis acid. The presence of lone pairs is confirmed from the 1c-2e AdNDP calculation. It is further noticed that the bulky group functionalized organo-Zintl cluster, [Ge-9(Bu-t)(3)](-) , can potentially act as a Lewis base and can make an intermolecular frustrated Lewis pair (FLP) with a well-known Lewis acid Tris[2,4,6-tris(trifluoromethyl)phenyl] borane, [B{C6H2(CF3)(3)}(3)].
THEORETICAL CHEMISTRY ACCOUNTS
(2023)
Article
Polymer Science
Meng Wang, Jordan Holland, Thomas A. R. Horton, Utku Yolsal, Michael P. Shaver
Summary: The versatile chemistry of boronic acid and boronate ester containing polymers has led to key applications in drug delivery, chemical sensing, and dynamic materials. In this paper, a novel fluorinated borinate ester copolymer was synthesized, which, when combined with a suitable Lewis basic copolymer, generated polymeric FLP networks capable of responsive gelation. The physical parameters and nature of the crosslinks of the gels prepared from different crosslinkers were probed by rheology, demonstrating strong elastic behavior and covalently crosslinked materials.
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
Chaohuang Chen, Constantin G. Daniliuc, Gerald Kehr, Gerhard Erker
Summary: The neutral N-heterocyclic carbene stabilized boranotsignalkene 1, prepared by a BH borenium/hydroboration method, can form stable copper, gold, or palladium pi-complexes. The polar boranotsignalkene B=C system undergoes selective hydroboration reactions with (C6F5)(2)BH or C6F5BH2 center dot SMe2 boranes. The latter reaction involves subsequent rearrangement leading to the exchange of internal hydride and isothiocyanate substituents at the borane pair.
CHEMISTRY-A EUROPEAN JOURNAL
(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
Multidisciplinary Sciences
Huamin Wang, Huiling Shao, Ankita Das, Subhabrata Dutta, Hok Tsun Chan, Constantin Daniliuc, K. N. Houk, Frank Glorius
Summary: In this study, a photoinduced ring enlargement method of thiophenes was developed, which involves the insertion of bicyclo[1.1.0]butanes to form eight-membered bicyclic rings under mild conditions. The synthetic value, broad functional-group compatibility, and excellent chemo- and regioselectivity were demonstrated by scope evaluation and product derivatization. Experimental and computational studies suggested a photoredox-induced radical pathway.
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)
