Dynamic covalent organocatalysts discovered from catalytic systems through rapid deconvolution screening

Area of Science:

• Organic Chemistry
• Catalysis
• Supramolecular Chemistry

Background:

• Dynamic covalent chemistry (DCC) enables the construction of adaptive and responsive molecular systems.
• Organocatalysts offer environmentally friendly alternatives to metal-based catalysts.
• The Morita-Baylis-Hillman (MBH) reaction is a valuable carbon-carbon bond-forming transformation.

Purpose of the Study:

• To report the first bifunctional organocatalyst assembled via DCC.
• To demonstrate the catalyst's efficacy in the MBH reaction.
• To showcase an in situ optimization strategy for dynamic catalysts.

Main Methods:

• Assembly of a bifunctional organocatalyst utilizing reversible imine chemistry.
• Application of the catalyst in the MBH reaction of enones with aldehydes or N-tosyl imines.
• Systemic screening and dynamic deconvolution for catalyst optimization.

Main Results:

• The DCC-assembled catalyst effectively catalyzes the MBH reaction.
• A novel thiourea-catalyzed transimination process was identified.
• In situ evaluation and optimization of catalyst mixtures were achieved without isolation.

Conclusions:

• A new class of bifunctional organocatalysts based on DCC has been developed.
• The described optimization strategy allows for efficient discovery of potent catalysts.
• The findings open avenues for designing adaptable catalytic systems.