Markus Leutzsch
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View article: Square‐Planar Ruthenium Alkylidyne Complexes Undergo Stepwise Rather Than Concerted [2 + 2] Cycloadditions with Alkynes
Square‐Planar Ruthenium Alkylidyne Complexes Undergo Stepwise Rather Than Concerted [2 + 2] Cycloadditions with Alkynes Open
A new entry into square‐planar, formally d 4 ‐configured ruthenium alkylidyne complexes is disclosed, using p ‐tolyl(trimethylsilyl)diazomethane as a convenient and safe alkylidyne synthon. The method furnished complex 12 supported by an e…
View article: Square‐Planar Ruthenium Alkylidyne Complexes Undergo Stepwise Rather Than Concerted [2 + 2] Cycloadditions with Alkynes
Square‐Planar Ruthenium Alkylidyne Complexes Undergo Stepwise Rather Than Concerted [2 + 2] Cycloadditions with Alkynes Open
A new entry into square‐planar, formally d 4 ‐configured ruthenium alkylidyne complexes is disclosed, using p ‐tolyl(trimethylsilyl)diazomethane as a convenient and safe alkylidyne synthon. The method furnished complex 12 supported by an e…
View article: Catalytic Enantioselective Diels–Alder Reaction of Dienes with Acyclic and α,β- and β,β-Disubstituted Enones
Catalytic Enantioselective Diels–Alder Reaction of Dienes with Acyclic and α,β- and β,β-Disubstituted Enones Open
Despite the wealth of methods to enantioselectively catalyze Diels-Alder reactions of α,β-unsaturated carbonyl dienophiles, until today, not a single example with an acyclic enone that is either β,β- or α,β-disubstituted has been reported.…
View article: Catalytic Asymmetric (<i>ene</i>–<i>endo</i>)-Carbonyl–Ene Type Cyclizations
Catalytic Asymmetric (<i>ene</i>–<i>endo</i>)-Carbonyl–Ene Type Cyclizations Open
The carbonyl-ene reaction between aldehydes and olefins constitutes a perfectly atom economic approach to homoallylic alcohols with concomitant C-C bond formation. However, the scope of catalytic asymmetric intermolecular versions is curre…
View article: Catalytic Asymmetric Ionic Hydrogenation of α-Alkyl Styrenes
Catalytic Asymmetric Ionic Hydrogenation of α-Alkyl Styrenes Open
Over the past two decades, chemists have made significant advances in the field of catalytic asymmetric transfer hydrogenation of various unsaturated compounds with biomimetic hydrogen donors. The reduction of carbon-carbon double bonds, h…
View article: Flash Communication: Bismuthinidenes as Lewis Bases in Reversible C(sp<sup>3</sup>)–O Bond Cleavage
Flash Communication: Bismuthinidenes as Lewis Bases in Reversible C(sp<sup>3</sup>)–O Bond Cleavage Open
Herein, we describe a unique example of a low-valent monocoordinated Bi-(I) complex acting as a Lewis base partner in a FLP activation reaction. The interplay between a bulky and rigid Bi-(I) and the Lewis acidic tris-(pentafluorophenyl)-b…
View article: 2-Substituted vs 2,9-Disubstituted Phenanthroline-Ni<sup>II</sup>-halides: Speciation Control and Structural Elucidation in Solution
2-Substituted vs 2,9-Disubstituted Phenanthroline-Ni<sup>II</sup>-halides: Speciation Control and Structural Elucidation in Solution Open
Herein we study the structures of selected 2,9-disubstituted and 2-monosubstituted phenanthroline NiII-dibromido and diiodido complexes via SC-XRD, SQUID magnetometry, UV-vis-NIR and DOSY NMR. In spite of the divergent speciation in solid …
View article: Catalytic 1,2‐Migratory Insertion in a Bismuth Redox Platform: Reductive Arylation of Aldehydes
Catalytic 1,2‐Migratory Insertion in a Bismuth Redox Platform: Reductive Arylation of Aldehydes Open
Herein, we report a catalytic defluorinative arylation of aldehydes with (per) A fluoroarenes facilitated by a pincer‐based PheBox‐Bi(I) under mild conditions. The protocol features various novel aspects in bismuth redox catalysis; namely,…
View article: Catalytic 1,2‐Migratory Insertion in a Bismuth Redox Platform: Reductive Arylation of Aldehydes
Catalytic 1,2‐Migratory Insertion in a Bismuth Redox Platform: Reductive Arylation of Aldehydes Open
Herein, we report a catalytic defluorinative arylation of aldehydes with (per) A fluoroarenes facilitated by a pincer‐based PheBox‐Bi(I) under mild conditions. The protocol features various novel aspects in bismuth redox catalysis; namely,…
View article: Isolation and Characterization of an Organobismuth Dihydride
Isolation and Characterization of an Organobismuth Dihydride Open
We report the synthesis, isolation, and structural characterization of an elusive organobismuth(III) dihydride (Ar*-Bi(III)-H2, 1). The complex features a bulky and rigid tBu-MsFluind ligand that permits complete spectroscopic characteriza…
View article: Deaminative Cyanation of Anilines by Oxylanion Radical Transfer
Deaminative Cyanation of Anilines by Oxylanion Radical Transfer Open
Herein, we report a straightforward methodology for direct deaminative cyanation of anilines via aryl diazonium salts as fleeting intermediates. The approach leverages the kinetic stability of nitrate and copper cyanide, iron's ability to …
View article: Pericyclic Umpolung in a Catalytic Asymmetric Diels–Alder Reaction of Tropone with Enol Ethers
Pericyclic Umpolung in a Catalytic Asymmetric Diels–Alder Reaction of Tropone with Enol Ethers Open
One remarkable feature of catalysis in chemical synthesis is its capacity to override substrate-imposed reactivity and selectivity. The inversion of normal reaction patterns, commonly known as Umpolung, can be divided into (1) functional g…
View article: A selenoxide for single-atom protein modification of tyrosine residues enabled by water-resistant chalcogen and hydrogen bonding
A selenoxide for single-atom protein modification of tyrosine residues enabled by water-resistant chalcogen and hydrogen bonding Open
Post-translational modifications such as phosphorylation and acetylation are often minor structural modifications that can have profound effects on protein structure and thus broaden protein functions. Nevertheless, studying these effects …
View article: Iron-Mediated Nitrate Reduction at Ambient Temperature for Deaminative Sulfonylation and Fluorination of Anilines
Iron-Mediated Nitrate Reduction at Ambient Temperature for Deaminative Sulfonylation and Fluorination of Anilines Open
Preparation of arylsulfonic acids and derivatives can be achieved under mild conditions from aryldiazonium salts, although conventional methods often require isolation or accumulation of these potentially hazardous intermediates. Herein, w…
View article: From Reagent to Catalyst: Dispersion-Driven Design of a General Asymmetric Transfer Hydrogenation Catalyst
From Reagent to Catalyst: Dispersion-Driven Design of a General Asymmetric Transfer Hydrogenation Catalyst Open
Even though chemists have long underappreciated the role of London dispersion in catalysis, its importance in determining a reaction course is now well recognized. Dispersion interactions have been shown to stabilize transition states and …
View article: Tripodal Silanolate Ligands Expand [MoX<sub>3</sub>] Chemistry Beyond Its Traditional Borders
Tripodal Silanolate Ligands Expand [MoX<sub>3</sub>] Chemistry Beyond Its Traditional Borders Open
Homodimeric complexes [X3Mo≡MoX3] are commonplace, but in no case is the corresponding monomeric [MoX3] species known; conversely, none of the very rare monomeric complexes [MoX3] has the respective homodimeric analogue. This mutual exclus…
View article: Evaluating Nano‐Scale Shifts: Quantifying Mesopore Shrinkage in Porous Polymers via NMR Cryoporometry
Evaluating Nano‐Scale Shifts: Quantifying Mesopore Shrinkage in Porous Polymers via NMR Cryoporometry Open
Nanoporous materials synthesized in a wet‐chemical process often show different pore sizes in their as‐prepared state in the reaction solution and their dried state. Depending on the materials, these changes can be reversible or irreversib…
View article: 3-Center-3-Electron σ-Adduct Enables Silyl Radical Transfer below the Minimum Barrier for Silyl Radical Formation
3-Center-3-Electron σ-Adduct Enables Silyl Radical Transfer below the Minimum Barrier for Silyl Radical Formation Open
Transition-metal-catalyzed cleavage of the Si-H bond in silanes to yield silyl radicals requires substantial amounts of energy, which are commonly supplied by photons. For Rh(II) porphyrins, efficient hydrosilylation catalysis becomes acce…
View article: Regioselective Hydroformylation of an α,β‐Unsaturated Ester: Spectroscopic Studies on Catalytic Species and the Influence of Ligands on Regioselectivity
Regioselective Hydroformylation of an α,β‐Unsaturated Ester: Spectroscopic Studies on Catalytic Species and the Influence of Ligands on Regioselectivity Open
Hydroformylation of α,β‐unsaturated esters is an atom‐economical route towards aldehydes as precursors for pharmaceuticals. In this work, regioselective hydroformylation of an α,β‐unsaturated ester to the β‐aldehyde was initially re‐evalua…
View article: Bronsted Acid-Catalyzed Reduction of Furans
Bronsted Acid-Catalyzed Reduction of Furans Open
Bioderived furans play a pivotal role in advancing defossilized chemical pathways. The complete reduction of furans currently relies on impractical metal-catalyzed hydrogenations at high pressures and temperatures. In addition, the Birch r…
View article: Total Synthesis of the Marine Diterpenoids Caucanolide E and F by Alkyne <i>gem</i>‐Hydrogenation: Rigorous Reassignment of Two Almost Indistinguishable Diastereomers
Total Synthesis of the Marine Diterpenoids Caucanolide E and F by Alkyne <i>gem</i>‐Hydrogenation: Rigorous Reassignment of Two Almost Indistinguishable Diastereomers Open
As the spectra of the diastereomeric marine seco ‐cembranoids caucanolide E and F are almost identical, the isolation team had not been able to firmly assign their stereostructure. The puzzle has now been solved by a synthetic approach pre…
View article: Total Synthesis of the Marine Diterpenoids Caucanolide E and F by Alkyne <i>gem</i>‐Hydrogenation: Rigorous Reassignment of Two Almost Indistinguishable Diastereomers
Total Synthesis of the Marine Diterpenoids Caucanolide E and F by Alkyne <i>gem</i>‐Hydrogenation: Rigorous Reassignment of Two Almost Indistinguishable Diastereomers Open
As the spectra of the diastereomeric marine seco ‐cembranoids caucanolide E and F are almost identical, the isolation team had not been able to firmly assign their stereostructure. The puzzle has now been solved by a synthetic approach pre…
View article: Red-Light-Active <i>N,C,N-</i>Pincer Bismuthinidene: Excited State Dynamics and Mechanism of Oxidative Addition into Aryl Iodides
Red-Light-Active <i>N,C,N-</i>Pincer Bismuthinidene: Excited State Dynamics and Mechanism of Oxidative Addition into Aryl Iodides Open
Despite the progress made in the field of synthetic organic photocatalysis over the past decade, the use of higher wavelengths, especially those in the deep-red portion of the electromagnetic spectrum, remains comparatively rare. We have p…
View article: Asymmetric <i>gem</i>‐Hydroboration and <i>gem</i>‐Hydrogenation of Ynamides: A New Gateway to Chiral Fischer Carbene Complexes and their Catalytic Transformations
Asymmetric <i>gem</i>‐Hydroboration and <i>gem</i>‐Hydrogenation of Ynamides: A New Gateway to Chiral Fischer Carbene Complexes and their Catalytic Transformations Open
Ynamides, when reacted with H 2 or HBpin in the presence of [Cp*RuCl] 4 , convert into chiral‐at‐metal Fischer carbenes by regioselective gem ‐hydrogenation or gem ‐hydroboration of the polarized triple bond, respectively. gem ‐Hydroborati…
View article: Asymmetric <i>gem</i>‐Hydroboration and <i>gem</i>‐Hydrogenation of Ynamides: A New Gateway to Chiral Fischer Carbene Complexes and their Catalytic Transformations
Asymmetric <i>gem</i>‐Hydroboration and <i>gem</i>‐Hydrogenation of Ynamides: A New Gateway to Chiral Fischer Carbene Complexes and their Catalytic Transformations Open
Ynamides, when reacted with H 2 or HBpin in the presence of [Cp*RuCl] 4 , convert into chiral‐at‐metal Fischer carbenes by regioselective gem ‐hydrogenation or gem ‐hydroboration of the polarized triple bond, respectively. gem ‐Hydroborati…
View article: A trimetallic bismuth(I)-based allyl cation
A trimetallic bismuth(I)-based allyl cation Open
The chemistry of low-valent bismuth compounds has recently unlocked new concepts in catalysis and unique electronic structure fundamentals. In this work, we describe the synthesis and characterization of a highly reduced bismuth salt featu…
View article: 3-center-3-electron σ-Adduct Enables Silyl Radical Transfer Below the Minimum Barrier for Silyl Radical Formation
3-center-3-electron σ-Adduct Enables Silyl Radical Transfer Below the Minimum Barrier for Silyl Radical Formation Open
Transition-metal-catalyzed cleavage of the Si–H bond in silanes to yield silyl radicals requires substantial amounts of energy, which is commonly supplied by photons. For Rh(II) porphyrins, efficient hydrosilylation catalysis only becomes …
View article: 3-center-3-electron σ-Adduct Enables Silyl Radical Transfer Below the Minimum Barrier for Silyl Radical Formation
3-center-3-electron σ-Adduct Enables Silyl Radical Transfer Below the Minimum Barrier for Silyl Radical Formation Open
Transition-metal-catalyzed cleavage of the Si–H bond in silanes to yield silyl radicals requires substantial amounts of energy, which is commonly supplied by photons. For Rh(II) porphyrins, efficient hydrosilylation catalysis only becomes …
View article: Red-light Active N,C,N-Pincer Bismuthinidene: Excited State Dynamics and Mechanism of Oxidative Addition into Aryl Iodides
Red-light Active N,C,N-Pincer Bismuthinidene: Excited State Dynamics and Mechanism of Oxidative Addition into Aryl Iodides Open
Despite the progress made in the field of synthetic organic photocatalysis over the last decade, the use of higher wavelengths, especially those in the deep-red portion of the electromagnetic spectrum, remain comparatively rare. We have pr…
View article: Catalytic Asymmetric Cycloaddition of Olefins with In Situ Generated <i>N</i>-Boc-Formaldimine
Catalytic Asymmetric Cycloaddition of Olefins with In Situ Generated <i>N</i>-Boc-Formaldimine Open
Chiral 1,3-amino alcohols are ubiquitous structural motifs in natural products and active pharmaceutical ingredients. We present a highly enantioselective, inverse-electron-demand hetero-Diels-Alder reaction of olefins with in situ generat…