Discovery of photocatalytic reactions enabled by high-throughput experimentation

24 June 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


The discovery of photocatalysed reactions involving many different substrate classes has significantly expanded accessible chemical space. However, the rational design of new classes of photocatalytic reactions can be hindered by their mechanistic complexity. A high-throughput experimentation approach was harnessed to facilitate the discovery of photocatalytic reactions involving novel pairs of substrate classes. The approach enabled the discovery of an unprecedented dearomative [4+3] photocycloaddition-oxidation reaction, and the extension of a [2+2] photocycloaddition to new classes of alkene substrate. The [4+3] photocycloaddition-oxidation was optimised, and shown to enable the synthesis of many complex bridged scaffolds from imidazo[1,2-a]pyrimidines and alternative aromatic substrates. High-throughput experimentation may be a useful tool for discovering other synthetically useful transformations that are based on rich and underexplored photocatalysis reactivity.


high-throughput experimentation
reaction discovery

Supplementary materials

Supporting Information
The file contains a general experimental section; methods for high-throughput experimentation; details of the optimisation of the [4+3] cycloaddition; a description of all synthetic protocols and compound characterisation; and copies of NMR spectra for novel compounds.


Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.