The principle of controlling reactivity and chirality in biological systems is a fundamental principle, where a complex system of stimuli, enzymes and feedback loops control the natural processes. Through a combination of signal transduction pathways and signal amplification strategies, a significant biological response, such as insulin regulation, is observed from a small initial stimulus. Designing a synthetic mimic to these natural processes is an interesting albeit difficult proposition.<br/>A smart stimuli-responsive asymmetric catalytic system was conceived where different chiral products are produced dependent on an external stimulation. The system utilises the ligand acceleration of organometallic catalysts in the presence of tosylated diamine ligands. Two enantiomeric proligands with orthogonal stimuli-responsive triggers were designed and synthesised, which when triggered result in ligand release. This turns on the catalytic cycle, allowing for the selective synthesis of a single enantiomer product. Subsequent testing showed the high specificity of the stimuli for their triggers, high enantioselectivity and low background reactivity. Further exploration using various substrates, including electrochemically active and biologically relevant substrates, displayed the robustness and ubiquity of the smart system.

Stimuli-responsive asymmetric catalysis

2019 Fall National Meeting

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