Modulating the radical reactivity of phenyl radicals with the help of distonic charges: it is all about electrostatic catalysis

This manuscript reports the electrostatic nature of the modulation of H-abstraction reactivity of phenyl radicals by (positive and negative) distonic ions.

Peter J Derrick and the Grand Scale ‘Magnificent Mass Machine’ mass spectrometer at Warwick

The value of the Grand Scale ‘Magnificent Mass Machine’ mass spectrometer in investigating the reactivity of ions in the gas phase is illustrated by a brief analysis of previously unpublished work on metastable ionised n-pentyl methyl ether, which loses predominantly methanol and an ethyl radical, with very minor contributions for elimination of ethane and water. Expulsion of an ethyl radical is interpreted in terms of isomerisation to ionised 3-pentyl methyl ether, via distonic ions and, possibly, an ion-neutral complex comprising ionised ethylcyclopropane and methanol. This explanation is consistent with the closely similar behaviour of the labelled analogues, C3H7CH2CD2OCH3+. and C3H7CD2CH2OCH3+., and is supported by the greater kinetic energy release associated with loss of ethane from ionised n-propyl methyl ether compared to that starting from directly generated ionised 3-pentyl methyl ether.

The chemistry of amine radical cations produced by visible light photoredox catalysis

Amine radical cations are highly useful reactive intermediates in amine synthesis. They have displayed several modes of reactivity leading to some highly sought-after synthetic intermediates including iminium ions, α-amino radicals, and distonic ions. One appealing method to access amine radical cations is through one-electron oxidation of the corresponding amines under visible light photoredox conditions. This approach and subsequent chemistries are emerging as a powerful tool in amine synthesis. This article reviews synthetic applications of amine radical cations produced by visible light photocatalysis.