Proline-catalyzed aldol reactions have been developed as an important toolbox for the synthesis of valuable chiral intermediates, giving birth to asymmetric organocatalysis. Despite progress, their current applications are generally performed in highly polar solvents that are either difficult to remove or with low substrate/product solubility. In addition, prolines are often used as homogeneous organocatalysts in these solvents, thus, the recycling of catalyst for reuse is also challenging. To solve these problems, we develop a proline-based Pickering emulsion for asymmetric aldol reactions with high reactivity and selectivity. The emulsion was stabilized by proline-functionalized silica nanoparticles that are not only highly active in the presence of water but also easily recycled after the operation. Interestingly, their high stereoselectivity was not compromised after multiple reuse, i.e., >86 ee (enantiomeric excess) in the first and second use. With this demonstration, we prove the concept that efficient and selective aldol reactions are enabled by proline-based Pickering emulsions, which is a great and continuous contribution to the field of asymmetric organocatalysis.
Bibliografisk noteFunding Information:
We acknowledge the financial support from the Independent Research Fund Denmark (DFF) within the framework of the Sapere Aude leader program and thank the Novo Nordisk Foundation for its generous funding. Furthermore, we thank Parmeet Singh for experimental help and Andreas Worbs for SEM imaging. The use of the HZDR Ion Beam Center TEM facilities and the funding of TEM Talos by the German Federal Ministry of Education and Research (BMBF), Grant No. 03SF0451, in the framework of HEMCP are acknowledged.
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