Spatiotemporal Control of Amide Radicals During Photocatalysis

30 March 2020, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Despite the continuing popularity of radical reactions in organic synthesis, much remains to be explored in this area. Herein, we describe how spatiotemporal control can be exerted over the formation and reactivity of divergent exchangeable formamide radicals using nickel complexes with a semiconductor material (TiO2) under irradiation from near-UV–Vis light. Depending on the bipyridine ligand used and the quantity of the nickel complex that is hybridized on or nonhydridized over the TiO2 surface, these radicals selectively undergo substitution reactions at the carbon center of carbon–bromine bonds that proceed via three different pathways. As the scalable production of formamides from CO2 does not produce salt waste, these methods could add a new dimension to the search for carbon neutrality through the indirect incorporation of CO2 into organic frameworks.

Keywords

photocatalysis
semiconductor photocatalysis
Nickel catalyst
titania catalysts
P25
C–C coupling reaction
C–N coupling
Amide activation
formamides
aryl bromide substrates
spatiotemporal activity
carbon dioxide surrogate
Radical Reaction

Supplementary materials

Title
Description
Actions
Title
ESI ChemRxiv0327
Description
Actions

Supplementary weblinks

Comments

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.