Tandem reactions in self-sorted catalytic molecular hydrogels

Area of Science:

• Supramolecular Chemistry
• Catalysis
• Materials Science

Background:

• Designing functional supramolecular materials requires precise control over component interactions.
• Incompatible catalytic groups often interfere with each other, limiting their combined application in one-pot reactions.
• Self-assembly offers a powerful strategy for organizing molecular components into functional architectures.

Purpose of the Study:

• To develop catalytic gelators with self-sorting capabilities to spatially separate incompatible catalytic functionalities.
• To investigate the impact of self-sorting on the efficiency and selectivity of one-pot tandem reactions.
• To demonstrate the utility of supramolecular self-sorting in preventing interference between catalytic groups.

Main Methods:

• Synthesized catalytic gelators (SucVal8 and ProValDoc) with distinct self-assembling motifs.
• Utilized self-assembly to achieve spontaneous segregation of gelators into separate supramolecular fibers.
• Performed one-pot deacetalization-aldol tandem reactions using the self-sorted catalytic fibers.
• Compared the results with co-assembled systems lacking self-sorting.

Main Results:

• SucVal8 and ProValDoc self-sorted into distinct supramolecular fibers due to differing self-assembling motives.
• The spatial separation of incompatible carboxylic acid and proline catalytic groups prevented mutual interference.
• One-pot deacetalization-aldol tandem reactions achieved up to 85% efficiency and 90% enantioselectivity.
• Co-assembly of SucVal8 with a similar non-sorting hydrogelator (ProVal8) precluded self-sorting and tandem catalysis.

Conclusions:

• Self-sorting of catalytic gelators is an effective strategy to spatially segregate incompatible catalytic functions.
• This supramolecular approach enables highly efficient and enantioselective one-pot tandem reactions.
• The design of self-assembling motives is crucial for achieving controlled organization and preventing catalytic interference.