Ketone-Derived Pro-aromatic Reagents for Radical Group Transfer Reactions and Deconstructive Functionalizations

Dedicated to Prof. Dr. Evelyn Creencia on the occasion of her retirement from the Dept. of Chemistry, Mindanao State University – Iligan Institute of Technology.

Abstract

The recent prominence of ketones as handles for sp³-rich radicals has expanded the paradigm of synthetic utility of ketones, putting the ubiquitous functional group once again into the spotlight in recent years. One emerging strategy arose through ketone-derived pro-aromatic reagents in the form of dihydrobenzothiazoline (BTZ), dihydroquinazolinone (DHQZ), dihydropyrazole (DHP), and dihydro-1,2,4-triazole (DHT) as key intermediates for aromaticity-promoted C–C bond homolytic fission. The formed sp³-radicals could then participate in various radical functionalizations, including alkylations, arylations, olefination, alkynylation, silylations, amination, thiolation, and deuteration, among others, either in photocatalytic, thermal, or oxidative conditions. In this review, we highlight the implications and recent advances in using these pro-aromatic reagents in radical group transfer reactions and deconstructive functionalization.

1 Introduction

2 Aromatization-Driven C–C Bond Scission of Ketones

3 Photochemical Reactions of Ketone-Derived Pro-aromatic Reagents

4 Non-photochemical Reactions of Ketone-Derived Pro-aromatic Reagents

5 Conclusion and Future Outlook

Key words

aromatization - radicals - ketones - metallaphotoredox - photoredox - thermal - C–C bond activation

Publication History

Received: 22 September 2023

Accepted after revision: 23 October 2023

Accepted Manuscript online:
24 October 2023

Article published online:
27 November 2023

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