Article
Chemistry, Multidisciplinary
Hyehwang Kim, Zheng-wang Qu, Stefan Grimme, Nahil Al-Zuhaika, Douglas W. Stephan
Summary: The phosphino-phosphonium cations can react with alkynes through frustrated Lewis pair-type addition reactions, leading to phosphino-phosphination reactions. This reactivity can also be utilized to prepare dissymmetric cis-olefin-linked bidentate phosphines.
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
Yile Wu, Zhao Zhao, Ting Chen, Jingjie Tan, Zheng-Wang Qu, Stefan Grimme, Yufen Zhao, Douglas W. Stephan
Summary: This study discovered a new compound 1, which can react with Lewis acids and participate in FLP chemistry. The reactivity of this compound varies under different conditions, depending on the nature of the electrophile and nucleophile generated in solution.
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)
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
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
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
Yi-Chen Chan, Yuna Bai, Wen-Ching Chen, Hsing-Yin Chen, Chen-Yu Li, Ying-Yann Wu, Mei-Chun Tseng, Glenn P. A. Yap, Lili Zhao, Hsuan-Ying Chen, Tiow-Gan Ong
Summary: By utilizing benzyl alcohol as a co-modulator, carbodicarbene is transformed into a Frustrated Lewis Pair-like reactivity, showing enhanced catalytic activity in various chemical reactions. This unique catalytic reactivity differs significantly from conventional NHC carbenes, demonstrating a new approach in diversifying FLP reactivity with the use of co-modulators.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
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
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, Multidisciplinary
Lucas Wickemeyer, Israel Fernandez, Beate Neumann, Hans-Georg Stammler, Norbert W. Mitzel
Summary: The oxygen-bridged frustrated Lewis pairs (FLPs) underwent selective complexation with azobenzene under UV irradiation. The adduct of the second FLP was stable, while the adduct of the first FLP showed a [3,3]-rearrangement resembling ortho-benzidine. Similar rearrangements were observed with different para-substituted azobenzenes and di(2-naphthyl)diazene, but not with ortho-methylated azo compounds. The characterization of all adducts was done by multinuclear NMR spectroscopy and elemental analyses, and the rearrangement mechanism was explored using quantum-chemical calculations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Shubhajit Das, Roland C. Turnell-Ritson, Paul J. Dyson, Clemence Corminboeuf
Summary: Despite recent progress in the chemistry of frustrated Lewis pairs (FLPs), direct FLP-catalyzed hydrogenation of CO2 remains elusive. The authors propose a mapping method to link the chemical composition of FLPs with their activity in catalytic hydrogenation of CO2, and they experimentally validate a combination with high catalytic turnover.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Brandon L. Frenette, Eric Rivard
Summary: Frustrated Lewis pairs (FLPs) have been extensively studied in the field of chemistry. In addition to their use in small molecule activation reactions, FLPs also show promise as chelating ligands. Through a donor-acceptor approach, FLPs can stabilize low oxidation state centers and reactive molecular fragments, playing an important role in main group element chemistry.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Xinyue Tan, Huadong Wang
Summary: The concept of frustrated Lewis pair (FLP) chemistry has become a rich and fruitful research area, contributing significantly to the revival of main group chemistry. The design of catalytic systems based on the FLP concept has been successfully applied to organic synthesis and polymer chemistry.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Christoph Wallach, Felix S. Geitner, Antti J. Karttunen, Thomas F. Faessler
Summary: The unique three-dimensional structure of spherical, homoatomic nine-atom germanium clusters allows for various spatial arrangement of functional groups. Recent introduction of ligands with lone pairs and addition of boranyl group to the cluster featuring a Ge-B exo-cluster bond have expanded the possibilities in cluster chemistry. Quantum-chemical calculations have revealed the frustrated Lewis pair character of the boranyl-functionalized cluster.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Justin Dubbert, Marco Valtolina, Alexander Huber, Tim D. Scherz, Christoph Woelper, Constantin G. Daniliuc, Ofer Filiba, Saumik Sen, Igor Schapiro, Fabio Rizzo, Jens Voskuhl
Summary: In this study, a series of chlorinated bridged ethers with varying numbers of sulfur and oxygen atoms were synthesized and their tunable photophysical properties in different aggregated states were investigated.
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, Multidisciplinary
Johannes E. Erchinger, Reece Hoogesteger, Ranjini Laskar, Subhabrata Dutta, Carla Huempel, Debanjan Rana, Constantin G. Daniliuc, Frank Glorius
Summary: This article presents a new synthetic method that utilizes a photosensitizer to react sulfur fluoride compounds with alkenes, resulting in protected beta-amino sulfonyl fluorides. This method can be used to synthesize peptido sulfonyl fluorides, beta-ammonium sulfonates, and beta-sultams relevant in medicinal chemistry.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Guangying Tan, Fritz Paulus, Alessia Petti, Maxim-Aleksa Wiethoff, Anna Lauer, Constantin Daniliuc, Frank Glorius
Summary: A novel radical relay 1,4-carboimination between two distinct olefins with alkyl carboxylic acid-derived bifunctional oxime esters was achieved via energy transfer catalysis. The reaction showed high chemo- and regioselectivity, forming multiple C-C and C-N bonds in a single operation. This mild and metal-free method exhibited a broad substrate scope and excellent tolerance of sensitive functional groups, providing easy access to structurally diverse 1,4-carboiminated products. Furthermore, the obtained imines could be readily converted into valuable biologically relevant free gamma-amino acids.
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
Chemistry, Organic
Dawod Yousif, Luca Vaghi, Constantin G. Daniliuc, Riccardo Po, Antonio Papagni, Fabio Rizzo
Summary: The regioselective nitration of 9,9'-spirobifluorene under mild conditions is reported for the first time using Menke's and Crivello's conditions. The optimized protocol yields 2-nitro and 2,2'-dinitro-9,9'-spirobifluorene in 79% and 95% yield, respectively, and for the first time, 2,2',7-trinitro-9,9'-spirobifluorene with a yield of 66%. Additionally, the role of dinitrate salt in Crivello's protocol has now been clarified, opening up new possibilities in the preparation of functional materials.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Joel Haefliger, Louise Ruyet, Nico Stuebke, Constantin G. Daniliuc, Ryan Gilmour
Summary: In this article, a cascade reaction is validated to generate novel gem-difluorinated isosteres from 1,3-diaryl cyclobutanols in a single operation, utilizing the biological significance of partially saturated, fluorine-containing rings and the physicochemical advantages conferred by fluorination.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Jonas Elfert, Anup Bhunia, Constantin G. Daniliuc, Armido Studer
Summary: In this study, a radical transformation that enables intramolecular oxygen atom transfer to alkenes using the nitro functionality in nitroarenes as an oxygen donor is disclosed. The reaction proceeds via iron-catalyzed metal hydrogen atom transfer to alkenes and subsequent oxygenation, resulting in alkene hydration. Compared to intermolecular radical oxygenation, the intramolecular variant offers advantages, particularly in terms of diastereoselective radical hydration of conformationally flexible alkenes. The aryl moiety connecting the reactive NO2-functionality to the alkene substrate can be cleaved after oxygen transfer, yielding products derived from a formal diastereoselective intermolecular alkene hydration. Additionally, the resulting aniline entity after oxygen transfer can be used for the construction of nitrogen-containing heterocycles.
Article
Chemistry, Physical
Dasharath Kondhare, Xenia Heddinga, Simone Budow-Busse, Constantin Daniliuc, Frank Seela
Summary: The single-crystal X-ray structure of 5-aza-7-deaza-7-iodoguanine 2'-C-methylribonucleoside 1 is described, which was synthesized through stereoselective nucleobase anion glycosylation and subsequent deprotection. The CD-spectrum analysis of 1 revealed the significant impact of the iodo substituent on the molecule. A dye conjugate was generated by Suzuki-Miyaura cross-coupling of 1 with pyrene boronic acid, showing solvent dependent exciplex fluorescence.
JOURNAL OF MOLECULAR STRUCTURE
(2023)
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
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 TBHP as the oxidant has been developed for the synthesis of quinoline-based p-extended polyheterocyclic compounds. This method allows the preparation of quinolines that are p-conjugated with an additional heteroarene moiety in a single sequence.
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)
