Direct Zinc(II)‐Catalyzed Enantioconvergent Additions of Terminal Alkynes to α‐Keto Esters

The addition of terminal alkynes to racemic β‐stereogenic α‐keto esters was achieved in high levels of stereoselectivity, affording versatile tertiary propargylic alcohols containing two stereocenters. This environmentally benign enantioconvergent reaction proceeds with perfect atom economy, requires no solvent, and is catalyzed by a non‐toxic zinc salt. The alkyne moiety can be leveraged in downstream transformations including hydrogenation to the corresponding saturated tertiary alcohol, which represents the product of a formal enantioconvergent aliphatic nucleophile addition.     

Cooperative Multifunctional Catalysts for Nitrone Synthesis: Platinum Nanoclusters in Amine‐Functionalized Metal–Organic Frameworks

Nitrones are key intermediates in organic synthesis and the pharmaceutical industry. The heterogeneous synthesis of nitrones with multifunctional catalysts is extremely attractive but rarely explored. Herein, we report ultrasmall platinum nanoclusters (PtNCs) encapsulated in amine‐functionalized Zr metal–organic framework (MOF), UiO‐66‐NH₂ (Pt@UiO‐66‐NH₂) as a multifunctional catalyst in the one‐pot tandem synthesis of nitrones. By virtue of the cooperative interplay among the selective hydrogenation activity provided by the ultrasmall PtNCs and Lewis acidity/basicity/nanoconfinement endowed by UiO‐66‐NH₂, Pt@UiO‐66‐NH₂ exhibits remarkable activity and selectivity, in comparison to Pt/carbon, Pt@UiO‐66, and Pd@UiO‐66‐NH₂. Pt@UiO‐66‐NH₂ also outperforms Pt nanoparticles supported on the external surface of the same MOF (Pt/UiO‐66‐NH₂). To our knowledge, this work demonstrates the first examples of one‐pot synthesis of nitrones using recyclable multifunctional heterogeneous catalysts.     

Self‐Generation of Surface Roughness by Low‐Surface‐Energy Alkyl Chains for Highly Stable Superhydrophobic/Superoleophilic MOFs with Multiple Functionalities

We transformed the hydrophilic metal–organic framework (MOF) UiO‐67 into hydrophobic UiO‐67‐R s (R=alkyl) by introducing alkyl chains into organic linkers, which not only protected hydrophilic Zr₆O₈ clusters to make the MOF interspace superoleophilic, but also led to a rough crystal surface beneficial for superhydrophobicity. The UiO‐67‐R s displayed high acid, base, and water stability, and long alkyl chains offered better hydrophobicity. Good hydrophobicity/oleophilicity were also possible with mixed‐ligand MOFs containing metal‐binding ligands. Thus, a (super)hydrophobic MOF catalyst loaded with Pd centers efficiently catalyzed Sonogashira reactions in water at ambient temperature. Studies of the hydrophobic effects of the coordination interspace and the outer surface suggest a simple de novo strategy for the synthesis of superhydrophobic MOFs that combine surface roughness and low surface energy. Such MOFs have potential for environmentally friendly catalysis and water purification.     

Atomic‐Scale Observation of the Metal–Promoter Interaction in Rh‐Based Syngas‐Upgrading Catalysts

The direct conversion of syngas to ethanol, typically using promoted Rh catalysts, is a cornerstone reaction in CO₂ utilization and hydrogen storage technologies. A rational catalyst development requires a detailed structural understanding of the activated catalyst and the role of promoters in driving chemoselectivity. Herein, we report a comprehensive atomic‐scale study of metal–promoter interactions in silica‐supported Rh, Rh–Mn, and Rh–Mn–Fe catalysts by aberration‐corrected (AC) TEM. While the catalytic reaction leads to the formation of a Rh carbide phase in the Rh–Mn/SiO₂ catalyst, the addition of Fe results in the formation of bimetallic Rh–Fe alloys, which further improves the selectivity and prevents the carbide formation. In all promoted catalysts, Mn is present as an oxide decorating the metal particles. Based on the atomic insight obtained, structural and electronic modifications induced by promoters are revealed and a basis for refined theoretical models is provided.