Mechanistic studies and high throughput kinetic experimentation in homogeneous catalysis

These empirical insights guided the development of a theoretical catalytic cycle which identified a unique mechanism of stereoselectivity, where pendant migrating groups are responsible for high levels of counter-intuitive product formation originating from the migratory insertion step.<br><br>Chapter three realizes Simulated Progress Kinetic Analysis as a viable method of kinetic profiling, negating intrinsic reaction time as a barrier to efficient workflows in kinetic experimentation.

Differential rate data was obtained directly using this technique in tandem with an automated flow chemistry platform, where liquid-liquid segmented flow was paramount to the success of this technology. Insights comparable to those established in the literature regarding the organocatalytic aldol reaction were replicated under non-steady-state conditions, where catalyst deactivation remained operative, and successful findings at multiple levels of experimental data density were achieved.

A first-of-its-kind, quasi high throughput, kinetic experimentation campaign explored chemical space in the transformation, with all findings being consistent with the accepted mechanistic model for familial reactions, and experimentation completed in a fraction of the time, material, and labour that would be typically demanded for such endeavors. Whilst promising, the limitations of this technique were considered, with many of them attributed to current hardware limitations in chemical robotics and process analytical technologies.

Collectively, this platform serves as a promethean approach to truly high throughput kinetic experimentation and is capable of accessing an unprecedented degree of experimentation.