Publication data for: "Class-II-aldolase-mimicking polyfunctional Lewis acid/azolium-aryloxide catalysts in direct enantioselective nitro-aldol additions"

This dataset provides the underlying experimental and computational research data for the publication "Class-II-aldolase-mimicking polyfunctional Lewis acid/azolium-aryloxide catalysts in direct enantioselective nitro-aldol additions".

Data type and creation: The dataset comprises analytical and spectroscopic measurements (NMR, HRMS, IR, UV-Vis, CD, SQUID, EPR) as well as chromatographic data (HPLC) generated during the synthesis and evaluation of novel Cobalt(II)-based catalysts. Additionally, it contains theoretical data derived from density functional theory (DFT) calculations (using Turbomole) and microkinetic modeling (using Julia).

Data structure: The data is systematically organized into directories corresponding to the applied analytical and computational methods.

Data interpretation: NMR, IR, and mass spectrometry data confirm the structural identity and purity of the synthesized compounds. HPLC chromatograms allow for the quantification of the enantiomeric excesses of the catalytic nitro-aldol products. The spectroscopic, magnetic, and computational data collectively elucidate the electronic properties of the Co(II) complexes and support the proposed class-II-aldolase-mimicking reaction mechanism.

Reuse potential: This dataset can be reused by other researchers to reproduce the experimental and theoretical results, or to use the spectra and chromatograms as reference material for related compounds. Furthermore, the provided computational coordinates, energies, and kinetic parameters offer a valuable basis for future theoretical benchmarking, machine learning applications in chemistry, or the design of new polyfunctional catalytic systems.

Abstract:
The catalytic asymmetric nitroaldol reaction is a powerful tool for accessing chiral 1,2-difunctionalized motifs, and numerous catalytic systems have been reported. Despite considerable progress in achieving high levels of stereocontrol, key challenges persist. In particular, optimal selectivity often requires cryogenic conditions, resulting in prolonged reaction times and limited practicality. In this article, a novel concept for asymmetric nitroaldol additions is introduced through a polyfunctional catalyst. This system integrates a Lewis acid, Co(II), with an azolium–aryloxide betaine, and exhibits mechanistic features reminiscent of class-II aldolases. The proposed mode of action is supported by comprehensive DFT calculations, microkinetic simulations, and detailed spectroscopic analyses. By the unique synergistic interplay of the Lewis acidic metal center, the aryloxide as Brønsted base and the corresponding aromatic alcohol serving as both hydrogen bond donor and Brønsted acid, high stereoselectivity was accomplished even at slightly elevated temperature for MeNO2. Like in class-II-aldolases, the aldehyde is activated by H-bonding to the aromatic alcohol and not by the Lewis acid. The latter serves to stabilize and direct the nitronate. The computational studies further demonstrate that the catalyst‘s key functional groups precisely orchestrate all accompanying transformations. As a result of the mild reaction conditions, not necessitating the use of an external base, the method also proved to be applicable to readily enolizable aliphatic aldehydes, such as phenylacetaldehyde.