Publications de Nicolai Cramer

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We found that cyclometalated cyclopentadienyl iridium(III) complexes are uniquely efficient catalysts in homogeneous hydrogenation of oximes to hydroxylamine products. A stable iridium C,N-chelation is crucial, with alkoxy-substituted aryl ketimine ligands ...

1,3,2-diazaphospholene hydrides (DAP-H) enable smooth conjugate reduction of polarized double bonds. The transiently formed phosphorus-enolate provides a potential platform for reductive alpha-functionalizations. In this respect, asymmetric C-heteroatom bo ...

The potent nucleophilicity and remarkably low basicity of 1,3,2- diazaphospholenes (DAPs) is exploited in a catalytic, metal-free 1,4-reduction of free ,-unsaturated carboxylic acids. Notably, the reduction occurs without a prior deprotonation of the car ...

Asymmetric hydrogenations are among the most practical methods for the synthesis of chiral building blocks at industrial scale. The selective reduction of an oxime to the corresponding chiral hydroxylamine derivative remains a challenging variant because o ...

Group 9 metals, in particular Rh III complexes with cyclopentadienyl ligands, are competent C–H activation catalysts. Recently, a Cp*Rh III catalyzed reaction of alkenes with N -enoxyphthalimides showed divergent outcome based on the solvent, with carboami ...

Chiral cyclic alkyl amino carbenes (CAACs), an intriguing subclass of N-heterocyclic carbenes, hold promising potential in asymmetric catalysis. Yet, synthetic hurdles and a lack of understanding of dominant selectivity-inducing design elements prevent the ...

Achieving substrate generality in asymmetric catalysis remains a long-standing goal, particularly for the selective construction of chiral heteroatoms. Compared with carbon, sulfur, phosphorus and silicon stereogenic centres, methods for the construction o ...

Despite advances in the synthesis of polysubstituted cyclopentadienyl metal complexes, the rapid access to a library of monosubstituted Cp bearing metal complexes remains challenging. A convenient and general method to access a broad range of monosubstitut ...

The development of unconventional ligand scaffolds is an important aspect to alter reaction pathways of transition-metal-catalyzed reactions. The nature of the counterion of cationic metal complexes plays an important role in the catalyst reactivity. We he ...

Catalytic enantioselective C-H functionalization has recently become a tool for the creation of stereogenic centers. The steep increase in molecular complexity of multicomponent reactions matches very well with asymmetric C-H functionalizations, but the re ...

Chiral carbon-carbon (C-C) and carbon-heteroatom (C-X) bonds are pervasive and very essential in natural products, bioactive molecules, and functional materials, and their catalytic construction has emerged as one of the hottest research fields in syntheti ...

Metal-catalyzed functionalizations at the ortho position of a directing group have become an efficient bond-forming strategy. A wide range of transformations that employ Cp*Rh-III catalysts have been described, but despite their synthetic potential, enanti ...

P-Hydrido 1,3,2-diazaphospholenes (DAPs) are a class of nucleophilic molecular hydrides capable of addition to a variety of substrates. They can be turned over with terminal reductants and emerged over the last few years as powerful and versatile catalysts ...

The direct and enantioselective functionalization of inert bonds such as carbon-hydrogen and carbon-carbon is an emerging tool towards more sustainable and efficient synthetic methods. The individual activation pathways like concerted deprotonation metalat ...

Asymmetric N-heterocyclic carbene (NHC) organocatalysis is a cornerstone of synthetic organic chemistry. The emerging concept of single-electron NHC catalysis broadened the scope of C-C bond-forming reactions, facilitating the synthesis of a variety of att ...

The electronic and steric properties of tailored cyclopentadienyl (Cp) ligands are powerful handles to modulate the catalytic properties of their metal complexes. This requires the individual preparation, purification and storage of each ligand/metal combi ...

Enantioselective carboaminations of olefins constitute an attractive strategy for a rapid increase in molecular complexity from readily available starting materials. Reported here is an intermolecular asymmetric carboamination of acrylates using rhodium(II ...

Vinyl triazenes were obtained by enantioselective [2+2] cycloaddition reactions of bicyclic alkenes with 1-alkynyl triazenes in the presence of a RuII catalyst with a chiral cyclopentadienyl ligand. These triazenes serve as unique vinyl cation surrogates. ...

Selective cleavages of carbon-carbon bonds catalyzed by transition-metal complexes have been shown to be increasingly versatile tools for organic synthesis allowing for complementary synthetic strategies. Numerous examples of transition-metal catalyzed C-C ...

The exploitation of strain release in small rings as driving force to enable complex transformations is a powerful synthetic tool. Among them, cyclobutanones are particularly versatile substrates that can be elaborated in a wide variety of structurally div ...

Nicolai Cramer

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Iridium-Catalyzed Acid-Assisted Hydrogenation of Oximes to Hydroxylamines

Reductive Asymmetric Aza-Mislow-Evans Rearrangement by 1,3,2-Diazaphospholene Catalysis

1,3,2‐Diazaphospholenes Catalyze the Conjugate Reduction of Substituted Acrylic Acids

Iridium-catalyzed acid-assisted asymmetric hydrogenation of oximes to hydroxylamines

Mapping Catalyst‐Solvent Interplay in Competing Carboamination/Cyclopropanation Reactions

Systematic Synthesis of Chiral CAACs with Three Independent Stereogenic Centers for Enantioselective Copper-Catalyzed Conjugate Borylation of Michael Acceptors

Accessing Carbon, Boron and Germanium Spiro Stereocentres in a Unified Catalytic Enantioselective Approach

Accessing Monosubstituted Cyclopentadienyl Rhodium(I) and Iridium(I) Complexes by a Simultaneous Nucleophilic Addition-Metalation Approach to Fulvenes

Asymmetric Rhodium(I)-Catalyzed C-C Activations with Zwitterionic Bis-phospholane Ligands

Cobalt(III)-Catalyzed Diastereo- and Enantioselective Three-Component C-H Functionalization

Recent advances in Rh(I)-catalyzed enantioselective C-H functionalization

Chiral Cp-Rhodium(III)-Catalyzed Asymmetric Hydroarylations of 1,1-Disubstituted Alkenes

Stay positive: catalysis with 1,3,2-diazaphospholenes

Catalytic Asymmetric Functionalization of Inert Bonds and Synthesis of Bioactive Natural Products

Tunable Thiazolium Carbenes for Enantioselective Radical Three-Component Dicarbofunctionalizations

A β-Carbon elimination strategy for convenient in situ access to cyclopentadienyl metal complexes

Enantioselective (CpRhIII)-Rh-x-Catalyzed Carboaminations of Acrylates

Divergent Asymmetric Synthesis of Polycyclic Compounds via Vinyl Triazenes

Catalytic C-C Bond Activations via Oxidative Addition to Transition Metals

Regiodivergent Cyclobutanone Cleavage: Switching Selectivity with Different Lewis Acids