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

Totan Mondal; Sason Shaik; Hilkka Kenttämaa; Thijs Stuyver

doi:10.1039/d0sc07111k

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

Chemical Science ◽

10.1039/d0sc07111k ◽

2021 ◽

Vol 12 (13) ◽

pp. 4800-4809

Author(s):

Totan Mondal ◽

Sason Shaik ◽

Hilkka Kenttämaa ◽

Thijs Stuyver

Keyword(s):

Phenyl Radicals ◽

Radical Reactivity ◽

Distonic Ions

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

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Charge-Site Effects on the Radical Reactivity of Distonic Ions†

The Journal of Physical Chemistry A ◽

10.1021/jp025521i ◽

2002 ◽

Vol 106 (42) ◽

pp. 9767-9775 ◽

Cited By ~ 23

Author(s):

Christopher J. Petzold ◽

Eric D. Nelson ◽

Harvey A. Lardin ◽

Hilkka I. Kenttämaa

Keyword(s):

Site Effects ◽

Charge Site ◽

Radical Reactivity ◽

Distonic Ions

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Recent advances in Minisci-type reactions and applications in organic synthesis

Current Organic Chemistry ◽

10.2174/1385272824999201230211157 ◽

2020 ◽

Vol 24 ◽

Author(s):

Wengui Wang ◽

Shoufeng Wang

Keyword(s):

Free Radical ◽

Hydrogen Atom ◽

Organic Synthesis ◽

Radical Reactivity ◽

Atom Loss ◽

Radical Generation ◽

In Situ Generation ◽

Thermal Cleavage ◽

Synthetic Chemist

Abstract:: Minisci-type reactions have become widely known as reactions that involve the addition of carbon-centered radicals to basic heteroarenes followed by formal hydrogen atom loss. While the originally developed protocols for radical generation remain in active use today, in recent years by a new array of radical generation strategies allow use of a wider variety of radical precursors that often operate under milder and more benign conditions. New transformations based on free radical reactivity are now available to a synthetic chemist looking to utilize a Minisci-type reaction. Radical-generation methods based on photoredox catalysis and electrochemistry, which utilize thermal cleavage or the in situ generation of reactive radical precursors, have become popular approaches. Our review will cover the remarkably literature that has appeared on this topic in recent 5 years, from 2015-01 to 2020-01, in an attempt to provide guidance to the synthetic chemist, on both the challenges that have been overcome and applications in organic synthesis.

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