Publications by Nicolai Cramer

Enantioselective acyl-trifluoromethylation of olefins by bulky thiazolium carbene catalysis

Enantioenriched α-chiral β-fluorinated ketones are valuable structural motifs with application in several fields. The recently emerged concept of NHC-catalyzed radical acyl-trifluoromethylation of olefins offers a rapid route to construct racemic β-fluorin ...

2025

Enantioselective Cobalt(III)-Catalyzed [4 + 1] Annulation of Benzamides: Cyclopropenes as One-Carbon Synthons

Matthew Wodrich, Nicolai Cramer

A chiral cyclopentadienyl cobalt(III)-catalyzed enantioselective [4 + 1] annulation of N-chlorobenzamides with cyclopropenes is reported. The cobalt catalyst engages in the C−H activation as well as promotes the C−C bond cleavage of the cyclopropene, rende ...

American Chemical Society (ACS)2025

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

Nicolai Cramer, Adrien Jules Louis Madron Du Vigné

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 ...

American Chemical Society (ACS)2025

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

Anne-Sophie Chauvin, Nicolai Cramer

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 ...

NATURE PORTFOLIO2025

Enantiospecific Synthesis of Planar Chiral Rhodium and Iridium Cyclopentadienyl Complexes: Enabling Streamlined and Computer-Guided Access to Highly Selective Catalysts for Asymmetric C-H Functionalizations

Rosario Scopelliti, Anne-Clémence Corminboeuf, Matthew Wodrich, Nicolai Cramer, Farzaneh Fadaei Tirani, Aragorn Nathan Laverny, Rubén Laplaza Solanas

Chiral cyclopentadienyl (CpX) metal complexes are frequently used in asymmetric catalysis by virtue of their high reactivity and selectivity. Planar-chiral-only rhodium and iridium cyclopentadienyl complexes are particularly promising due to unrestricted c ...

2024

Tunable Thiazolium Carbenes for Enantioselective Radical Three-Component Dicarbofunctionalizations

Nicolai Cramer

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 ...

AMER CHEMICAL SOC2024

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

Nicolai Cramer, Shouguo Wang, Yi Zhang, Zhen Chen

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 ...

Royal Society of Chemistry2024

Catalytic enantioselective reductive Eschenmoser-Claisen rearrangements

Matthew Wodrich, Nicolai Cramer

An important challenge in enantioselective catalysis is developing strategies for the precise synthesis of neighboring congested all-carbon quaternary stereocenters. The well-defined transition states of [3,3]-sigmatropic rearrangements and their underlyin ...

American Association for the Advancement of Science2024

Streamlined synthetic assembly of α-chiral CAAC ligands and catalytic performance of their copper and ruthenium complexes

Nicolai Cramer, Adrien Jules Louis Madron Du Vigné

The unique electronic and steric parameters of chiral cyclic alkyl amino carbene (CAAC) ligands render them appealing steering ligands for enantioselective transition-metal catalyzed transformations. Due to the lack of efficient synthetic strategies to acc ...

2024

Nickel-catalyzed direct stereoselective α-allylation of ketones with non-conjugated dienes

Matthew Wodrich, Nicolai Cramer

The development of efficient and sustainable methods for the construction of carbon-carbon bonds with the simultaneous stereoselective generation of vicinal stereogenic centers is a longstanding goal in organic chemistry. Low-valent nickel(0) complexes whi ...

Nature Research2023

Swiss CAT plus , a Data-driven Infrastructure for Accelerated Catalysts Discovery and Optimization

Pascal Miéville, Florian Patrick Marie Daniel De la Barre De Nanteuil, Nicolai Cramer

The Catalysis Hub - Swiss CAT+, is a new infrastructure project funded by the ETH Domain, co -head-ed by EPFL and ETHZ. It offers the scientific community a unique integrated technology platform combining automated and high-throughput experimentation with ...

SWISS CHEMICAL SOC2023

Toward in silico Catalyst Optimization

Anne-Clémence Corminboeuf, Matthew Wodrich, Nicolai Cramer, Rubén Laplaza Solanas

In this minireview, we overview a computational pipeline developed within the framework of NCCR Catalysis that can be used to successfully reproduce the enantiomeric ratios of homogeneous catalytic reactions. At the core of this pipeline is the SCINE Molas ...

SWISS CHEMICAL SOC2023

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

Nicolai Cramer

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 ...

Wiley-VCH Verlag GmbH2023

Mapping Catalyst‐Solvent Interplay in Competing Carboamination/Cyclopropanation Reactions

Anne-Clémence Corminboeuf, Matthew Wodrich, Nicolai Cramer, Miyeon Chang, Simone Gallarati

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 ...

2022

Chemo- and regio-divergent access to fluorinated 1-alkyl and 1-acyl triazenes from alkynyl triazenes

Kay Severin, Nicolai Cramer, Jin Fay Tan, Carl Thomas Bormann

The 1,1,2,2-tetrafluoroethylene unit is prevalent in bioactive molecules and functional materials. Despite being in principle a straightforward strategy to access this motif, the direct tetrafluorination of alkynes involves very hazardous or inconvenient r ...

2022

Enantioselective Access to 3-Azabicyclo[3.1.0]hexanes by (CpRhIII)-Rh-x Catalyzed C-H Activation and Cp*Ir-III Transfer Hydrogenation

Nicolai Cramer, Dan Forster, Coralie Danielle Annick Duchemin

Rigid saturated nitrogen-containing scaffolds such as 3-azabicyclo[3.1.0]hexanes are very important and frequently occurring motifs in biologically active compounds. We disclose a flexible two-step protocol for their efficient and selective access. A tailo ...

AMER CHEMICAL SOC2022

Chiral Cyclopentadienyl Ligands: Design, Syntheses, and Applications in Asymmetric Catalysis

Nicolai Cramer, Benoît Daniel Bertrand Audic, Aragorn Nathan Laverny

The creation of new chiral ligands capable of providing high stereocontrol in metal-catalyzed reactions is crucial in modern organic synthesis. The production of bioactive molecules as single enantiomers is increasingly required, and asymmetric catalysis w ...

Wiley-VCH Verlag GmbH2021

Atropo‐Enantioselective Oxidation‐Enabled Iridium(III)‐Catalyzed C−H Arylations with Aryl Boronic Esters

Nicolai Cramer

Atropo-enantioselective biaryl coupling through C−H bond functionalization is an emerging technology allowing direct construction of axially chiral molecules. This approach is largely limited to electrophilic coupling partners. We report a highly atropo-en ...

Wiley-VCH Verlag GmbH2021

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

Nicolai Cramer

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 ...

2021

Iridium-Catalyzed Acid-Assisted Hydrogenation of Oximes to Hydroxylamines

Nicolai Cramer

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 ...

Wiley-VCH Verlag GmbH2021