Frank Glorius

Frank Glorius
University of Münster | WWU · Institute of Organic Chemistry

Prof. Dr.

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646
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55,263
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Publications

Publications (646)
Preprint
Vicinal diamines, especially unsymmetrical ones, are among the most common structural motifs in biologically active molecules, natural products, and pharmaceuticals. While the catalytic diamination of carbon–carbon double bonds provides rapid access to diamines, these reactions are often limited to installing undifferentiated amino functionalities...
Article
The development of new strategies and concepts towards the synthetic utilization of carbonyl compounds is of pivotal relevance. Nevertheless, the generation of ketyl radicals requires relatively harsh conditions and a large excess of reductants, which represents a long-standing, unsolved problem that hampers the broad application of ketyl coupling...
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Full-text available
Ketyl-olefin coupling reactions stand as one of the fundamental chemical transformations in synthetic chemistry and have been widely employed in the generation of complex molecular architectures and natural product synthesis. However, catalytic ketyl-olefin coupling, until the recent development of photoredox chemistry and electrosynthesis through...
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Saturated N‐heterocycles are prominent motifs found in various natural products and pharmaceuticals. Despite the increasing interest in this class of compounds, the synthesis of saturated bicyclic azacycles requires tedious multi‐step syntheses. Herein, we present a one‐pot protocol for the synthesis of octahydroindoles, decahydroquinolines, and oc...
Article
A new class of saturated boron‐incorporated cyclic molecules has been synthesized employing an arene‐hydrogenation methodology. cis ‐Selective hydrogenation of easily accessible, and biologically important molecules comprising benzoxaborole, benzoxaborinin, and benzoxaboripin‐derivatives is reported. Among the various catalysts tested, rhodium cycl...
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For more than one century, photochemical [2+2]-cycloadditions have been used by synthetic chemists to make cyclobutanes, four-membered carbon-based rings. In this reaction, typically two olefin subunits (two π-electrons per olefin) cyclize to form two new C–C σ-bonds. Although the development of photochemical [2+2]-cycloadditions has made significa...
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Metabolic distribution of fatty acid to organelles is an essential biological process for energy homeostasis as well as for the maintenance of membrane integrity, and the metabolic pathways are strictly regulated in response to environmental stimuli. Herein, we report a fluorescent fatty acid probe, which bears an azapyrene dye that changes its abs...
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Assessing the outcomes of chemical reactions in a quantitative fashion has been a cornerstone across all synthetic disciplines. Classically approached through empirical optimization, data‐driven modelling bears an enormous potential to streamline this process. However, such predictive models require significant quantities of high‐quality data, the...
Article
Assessing the outcomes of chemical reactions in a quantitative fashion has been a cornerstone across all synthetic disciplines. Classically approached through empirical optimization, data‐driven modelling bears an enormous potential to streamline this process. However, such predictive models require significant quantities of high‐quality data, the...
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Full-text available
Hybrid fused two-dimensional/three-dimensional (2D/3D) rings are important pharmacophores in drugs owing to their unique structural and physicochemical properties. Preparation of these strained ring systems often requires elaborate synthetic effort and exhibits low efficiency, thus representing a limiting factor in drug discovery. Here, we report t...
Article
A new class of saturated boron‐incorporated cyclic molecules has been synthesized employing an arene‐hydrogenation methodology. cis ‐Selective hydrogenation of easily accessible, and biologically important molecules comprising benzoxaborole, benzoxaborinin, and benzoxaboripin‐derivatives is reported. Among the various catalysts tested, rhodium cycl...
Article
N‐Heterocyclic carbenes (NHCs) have superior properties as building blocks of self‐assembled monolayers (SAMs). Understanding the influence of the substrate in the molecular arrangement is a fundamental step before employing these ligands in technological applications. Herein, we study the molecular arrangement of a model NHC on Cu(100) and Cu(111)...
Article
N‐Heterocyclic carbenes (NHCs) have superior properties as building blocks of self‐assembled monolayers (SAMs). Understanding the influence of the substrate in the molecular arrangement is a fundamental step before employing these ligands in technological applications. Herein, we study the molecular arrangement of a model NHC on Cu(100) and Cu(111)...
Article
Improving signal-to-noise and, thereby, image contrast is one of the key challenges needed to expand the useful applications of mass spectrometry imaging (MSI). Both instrumental and data analysis approaches are of importance. Univariate denoising techniques have been used to improve contrast in MSI images with varying levels of success. Additional...
Article
The formation of carbon−carbon bonds lies at the heart of synthetic organic chemistry and is widely applied to construct complex drugs, polymers, and materials. Despite its importance, catalytic carbonyl arylation remains comparatively underdeveloped, due to limited scope and functional group tolerance. Herein we disclose an umpolung strategy to ac...
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Photocatalysis. In their Research Article (e202112344), Frank Glorius, Fabian Dielmann et al. present photoswitchable nitrogen superbases for reversible carbon dioxide capture.
Article
Photokatalyse. In ihrem Forschungsartikel (e202112344) präsentieren Frank Glorius, Fabian Dielmann et al. photoschaltbare Stickstoff-Superbasen für den reversiblen Kohlendioxid-Einfang.
Article
Transforming C(sp³)–H bonds efficiently and selectively into C(sp³)–C(sp³) or C(sp³)–X bonds is a highly relevant task. The direct arylation of allylic C(sp³)–H bonds provides an elegant method for the formation of unconjugated aryl-substituted olefins. Although both ionic- and radical-based transition metal catalysis has been applied to achieve th...
Article
Herein, a regioselective synthesis of indolizino[3,4,5- ab ]isoindoles (INIs), a valuable class of heterocycles with interesting luminescence properties, is described using manganese(I)-catalyzed C−H activation. The reported transformation proceeds in a one-step procedure...
Article
Self-assembly of cyclohexyl cyclic (alkyl)(amino)carbenes (cyCAAC) can be realized and reversibly switched from a close-packed trimer phase to a chainlike dimer phase, enabled by the ring-flip of the cyclohexyl wingtip. Multiple methods including scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS) and density functional theo...
Article
Self-assembly of cyclohexyl cyclic (alkyl)(amino)carbenes (cyCAAC) can be realized and reversibly switched from a close-packed trimer phase to a chainlike dimer phase, enabled by the ring-flip of the cyclohexyl wingtip. Multiple methods including scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS) and density functional theo...
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Full-text available
The chiral ruthenium(ii)bis-SINpEt complex is a versatile and powerful catalyst for the hydrogenation of a broad range of heteroarenes. This study aims to provide understanding of the active form of this privileged catalyst as well as the reaction mechanism, and to identify the factors which control enantioselectivity. To this end we used computati...
Article
Providing strong carbon-metal (C-M) bonds, N-heterocyclic carbenes (NHCs) recently were introduced as surface modifiers for various applications. Here we report a fluorinated NHC (F-NHC) monolayer chemically bonded to Au with...
Article
Selective C–F bond functionalization of perfluoalkyl units has huge potential towards accessing functionalized organofluorinated compounds, but remains chanllenging due to the high C–F bond strength and inherent selectivity challenges. We report a new catalytic approach for the selective functionalization of the strong C–F bonds in polyfluorinated...
Article
Control of selectivity is a pivotal challenge in radical chemistry owing to the high reactivity and instability of radical species. Herein, a switchable, base-controlled strategy toward the reincorporation/release of SO2 in photocatalyzed radical difunctionalization of alkenes has been described. By this chemodivergent strategy, a variety of valuab...
Article
Selective C–F bond functionalization of perfluoalkyl units has huge potential towards accessing functionalized organofluorinated compounds, but remains chanllenging due to the high C–F bond strength and inherent selectivity challenges. We report a new catalytic approach for the selective functionalization of the strong C–F bonds in polyfluorinated...
Article
Herein, we present a visible-light-mediated two-carbon ring expansion of β -dicarbonyl compounds with unactivated olefins providing facile access to medium-sized rings. Selective sensitization of the substoichiometric enol tautomer enables reactivity with substrates incompatible with the classical De Mayo-reaction conditions. Key to success is the...
Preprint
The allylation of aldehydes is a fundamental transformation in synthetic organic chemistry. Among the multitude of available reagents, especially allylsilanes have been established as preferred allyl source. As initially reported by Hosomi & Sakurai, these non-toxic and highly stable reagents add to carbonyls via an open transition state upon Lewis...
Preprint
The allylation of aldehydes is a fundamental transformation in synthetic organic chemistry. Among the multitude of available reagents, especially allylsilanes have been established as preferred allyl source. As initially reported by Hosomi & Sakurai, these non-toxic and highly stable reagents add to carbonyls via an open transition state upon Lewis...
Article
The development of a catalytic strategy for one-carbon homologation is of foundational importance in organic synthesis enabling quick elaboration of useful molecules. Herein, we report a dual nickel/photoredox catalytic strategy for transforming a range of α-amino acids into β-amino aldehydes in a simple one-step operation. This method provides a n...
Article
Herein, we present a visible‐light‐mediated two‐carbon ring expansion of β ‐dicarbonyl compounds with unactivated olefins providing facile access to medium‐sized rings. Selective sensitization of the substoichiometric enol tautomer enables reactivity with substrates incompatible with the classical De Mayo‐reaction conditions. Key to success is the...
Article
Using light as an external stimulus to alter the reactivity of Lewis bases is an intriguing tool for controlling chemical reactions. Reversible photoreactions associated with pronounced reactivity changes are particularly valuable in this regard. We herein report the first photoswitchable nitrogen superbases based on guanidines equipped with a dith...
Article
Archaeal lipids have harvested biomedical and biotechnological interest because of their ability to form membranes with low permeability and enhanced temperature and pressure stability. Because of problems in isolating archaeal lipids, chemical synthesis appears to be a suitable means of producing model lipids that mimic the biological counterparts...
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Full-text available
Using light as an external stimulus to alter the reactivity of Lewis bases is an intriguing tool for controlling chemical reactions. Reversible photoreactions associated with pronounced reactivity changes are particularly valuable in this regard. We herein report the first photoswitchable nitrogen superbases based on guanidines equipped with a dith...
Preprint
Full-text available
In response to pro-inflammatory challenges including pathogenic attack and tissue damage, the endothelial cell surface is rearranged to present leukocyte-engaging cell surface receptors. The initial contact needed for leukocyte tethering and rolling is mediated via adhesion demand-driven exocytosis of Weibel-Palade bodies (WPB) that contain the leu...
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The development of organic materials with high solid-state luminescence efficiency is highly desirable because of their fundamental importance and applicability in optoelectronics. Herein, a rapid construction of novel BF2 complexes with N,O-bidentate ligands by using Cu(BF4)2•6H2O as a catalyst and BF2 source is disclosed, which avoids the need fo...
Article
N-Heterocyclic carbenes, despite being isolated and characterized three decades ago, still capture scientists’ interest as versatile, modular and strongly coordinating moieties. In the last decade, driven by the increasingly refined fundamental understanding of their behaviour, the emergence of new carbene frameworks and cogent sustainability issue...
Article
Direct enantioselective hydrogenation of unsaturated compounds to generate chiral three‐dimensional motifs is one of the most straightforward and important approaches in synthetic chemistry. We realized the Ru(II)‐NHC catalyzed asymmetric hydrogenation of 2‐quinolones under mild reaction conditions. Alkyl, aryl and halogen substituted optically act...
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Full-text available
Direct enantioselective hydrogenation of unsaturated compounds to generate chiral three‐dimensional motifs is one of the most straightforward and important approaches in synthetic chemistry. We realized the Ru(II)‐NHC catalyzed asymmetric hydrogenation of 2‐quinolones under mild reaction conditions. Alkyl, aryl and halogen substituted optically act...
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Full-text available
N-Heterocyclic carbenes (NHCs) are promising modifiers and anchors for surface functionalization and offer some advantages over thiol-based systems. Because of their strong binding affinity and high electron donation, NHCs can dramatically change the properties of the surfaces to which they are bonded. Highly ordered NHC monolayers have so far been...
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Full-text available
Cholesterol is an essential component of cellular membranes regulating the structural integrity and fluidity of biological bilayers and cellular processes such as signal transduction and membrane trafficking. However, tools to investigate the role and dynamics of cholesterol in live cells are still scarce and often show limited applicability. To ad...
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The development of novel Lewis acids derived from bipyridinium and phenanthrolinium dications is reported. Calculations of Hydride Ion Affinity (HIA) values indicate high carbon‐based Lewis acidity at the ortho and para positions. This arises in part from extensive LUMO delocalization across the aromatic backbones. Species [C 10 H 6 R 2 N 2 CH 2 CH...
Article
Herein, we describe the formation of quaternary carbon centers with excellent diastereoselectivity via a strain-release protocol. An organometallic species is generated by Cp*Rh(III)-catalyzed C-H activation, which is then coupled with strained bicyclobutanes (BCBs) and a prochiral carbon electrophile in a three-component reaction. This work illust...
Article
Free-to-read link: https://rdcu.be/ckbGT Heterogeneous catalysts represent the backbone of many industrial processes and thus have a considerable societal impact. The active sites of these heterogeneous catalysts are often metal surfaces, which consist of a large ensemble of metal atoms, and their properties differ significantly from metal complex...
Article
The C-C bond formation reaction represents a fundamental and important transformation in synthetic chemistry, and exploring new types of C-C bond formation reactions is recognized as appealing, yet challenging. Herein, we disclose the first example of rhodium-catalyzed dealkenylative arylation of alkenes with arylboronic compounds, thereby providin...
Article
Eine Rhodium(III)-katalysierte Dealkenylierungs-Arylierung von Alkenen und 1,3-Dienen mit Arylboronverbindungen wurde entwickelt, um einen unkonventionellen Zugang zu Bi(hetero)arylen mit exzellenter Chemoselektivität zu schaffen. Abstract Die C-C-Bindungsbildungsreaktion stellt eine fundamentale und wichtige Transformation in der Synthesechemie d...
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We report a method for the enantioselective hydrogenation of annulated arenes using 4H-pyrido[1,2-a]pyrimidinones as substrates. The method selectively generates multiple stereocenters in adjacent rings leading to architecturally complex motifs, which resemble bioactive molecules. The mechanistic study of the stereochemical outcome revealed that th...
Article
Full paper via read-only Link: https://go.nature.com/2PW5SOU Developments in synthetic chemistry are increasingly driven by improvements in the selectivity and sustainability of transformations. Bifunctional reagents, either as dual coupling partners or as a coupling partner in combination with an activating species, offer an atom-economic approac...
Article
The polarity of all-cis-multifluorinated cyclohexanes can be fine-tuned by the number and relative orientation of fluoro substituents, giving rise to a series of compounds with strong dipole moments. Simulations provided the energetics, the dipole moments, and the respective molecular polarizabilities, while dielectric spectroscopy gave information...
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Full-text available
Die metallfreie Dearomatisierung von N‐Heteroaromaten ist eine bekannte und leistungsfähige Methode, um teilgesättigte N‐heterozyklische Bausteine zu erhalten. Die Verwendung empfindlicher Reagenzien schränkt jedoch die Anwendbarkeit im Labor ein. Hier wird eine sehr milde und selektive Reduktion von N‐Heteroaromaten mit Aminboran zur Synthese eine...
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Dearomatization is an effective method to transform readily available N‐heterocycles into partially saturated motifs. Manipulation of dihydro‐derivatives holds great potential and provides access to a variety of semi‐saturated N‐heterocyclic building blocks. However, current strategies are limited in scope and the use of sensitive reagents restrict...
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We report an enantio‐ and diastereoselective, complete hydrogenation of multiply substituted benzofurans in a one‐pot cascade catalysis. The developed protocol facilitates the controlled installation of up to six new defined stereocenters and produces architecturally complex octahydrobenzofurans, prevalent in many bioactive molecules. A unique matc...
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Eine katalytische Eintopf-Kaskadenhydrierung wurde entwickelt, mit der enantiomerenangereicherte Octahydrobenzofurane mit bis zu sechs neuen Stereozentren erhalten werden können. Der dualkatalytische, sequentielle Prozess wird ermöglicht durch ein einzigartiges Zusammenspiel eines chiralen Ruthenium-Carben-Katalysators und eines achiralen Rhodium-K...
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Dearomative cycloaddition reactions represent an ideal means of converting flat arenes into three-dimensional architectures of increasing interest in medicinal chemistry. Quinolines, isoquinolines, and quinazolines, despite containing latent diene and alkene subunits, are scarcely applied in cycloaddition reactions because of the inherent low react...
Article
Die Synthese von β-Lactamen aus α-Ketoacylsilanen und Iminen über eine photochemische [2+2]-Cycloaddition unter in situ-Generierung von Siloxyketenen durch eine [1,3]-Siliciumverschiebung wird beschrieben. Durch die Reaktion können verschiedene Substratklassen wie Aldiminen, Ketiminen, Hydrazonen, als auch wichtige β-Lactame mit guten Diastereosele...
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We report the synthesis of β ‐lactams from α‐ ketoacylsilanes and imines, which proceeds via a formal [2+2] photochemical cycloaddition with in situ generation of siloxyketene. This mild and operationally simple reaction proceeds in an atom‐economic fashion with broad substrate scope, including aldimines, ketimines, hydrazones, and fused nitrogen h...
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Since the definition of the “12 Principles of Green Chemistry” more than 20 years ago, chemists have become increasingly mindful of the need to conserve natural resources and protect the environment through the judicious choice of synthetic routes and materials. The direct activation and functionalization of C–H bonds, bypassing intermediate functi...
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Incorporation of silicon into negative electrodes is pursued widely to increase the energy density of lithium ion batteries (LIBs). However, severe volume changes of silicon during (de)lithiation cause consumption of active lithium and electrolyte by continuous solid electrolyte interphase (SEI) formation, resulting in deterioration of cell perform...
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Hydroarylation is an effective strategy to rapidly increase the complexity of organic structures by transforming flat alkene moieties into three‐dimensional frameworks. Many strategies have already been developed to achieve the hydroarylation of styrenes, however most of these reports examine the hydroarylation of unpolar, β‐mono‐ or β‐unsubstitute...
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Die Hydroarylierung ist effektiv, um die Komplexität organischer Strukturen schnell zu erhöhen, indem flache Alken‐Einheiten in 3D‐Gerüste umgewandelt werden. Eine neue Methode für die selektive Hydroheteroarylierung von mehrfach substituierten Styrolen und heteroaromatischen Styrolen liefert mehrfach ringsubstituierte Produkte. Kommerziell erhältl...
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Metal‐catalyzed hydrogenation is an effective method to transform readily available arenes into saturated motifs, however, current hydrogenation strategies are limited to the formation of C–H and N–H bonds. The stepwise addition of hydrogen yields reactive unsaturated intermediates that are rapidly reduced. In contrast, the interruption of complete...
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Die Metall‐katalysierte Hydrierung von Aromaten ist eine effiziente Transformation, um gesättigte Carbo‐ und Heterocyclen zu erhalten, die allerdings auf die Bildung von C‐H‐ und N‐H‐Bindungen beschränkt ist. Wir stellen hier die Synthese von enantioangereicherten δ‐Lactamen aus leicht verfügbaren Oxazolidinon‐substituierten Pyridinen vor. Entschei...
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Herein, we report the 1,2-dialkylation of simple feedstock acrylates for the synthesis of valuable tertiary carboxylic acids by merging Giese-type radical addition with an Ireland–Claisen rearrangement. Key to success is the utilization of the reductive radical-polar crossover concept under photocatalytic reaction conditions to force the [3,3]-sigm...
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Herein, we report a Cp*IrIII‐catalyzed highly regioselective and redox‐neutral protocol for the construction of 1,4‐enynes from unactivated olefins and bromoalkynes via intermolecular allylic C–H alkynylation. The developed mild reaction conditions tolerate a broad range of common functional groups, even enabling selective alkynylation of allylic C...
Article
Iridium‐Allyl‐Paar! Hierin beschreiben wir eine Cp*IrIII‐katalysierte hochregioselektive und redoxneutrale Alkinylierung von unaktivierten Olefinen mit Bromalkinen über allylische C‐H‐Aktivierung. Diese undirigierte C‐H‐Funktionalisierung war bevorzugt gegenüber anderen typischerweise verwendeten dirigierenden Gruppen, einschließlich Ketonen, Ester...