Photoredox-Catalysis-Enabled Ring-Opening Functionalization of Aryl Cyclopropanes

Abstract

Cyclopropanes have long been recognized as privileged synthons in organic synthesis, providing access to 1,3-difunctionalized scaffolds. However, the synthetic potential of aryl cyclopropanes, one of the most important subclasses of cyclopropanes, is far less explored. Recently, we uncovered a visible-light-promoted strategy for the ring-opening functionalization of a series of aryl cyclopropanes through open-shell intermediates. By leveraging the activation of an aryl radical cation derived from an oxidative single-electron transfer, the C–C bond of the cyclopropane is weakened and cleaves upon a regio- and stereoselective nucleophilic attack with an exogenous nucleophile to provide a benzyl radical that can be readily elaborated to diverse functionalities.

1 Introduction

2 Core Concept of Our Design

3 Photoredox-Catalyzed Oxoamination of Aryl Cyclopropanes

4 Photoredox-Catalyzed Hydroheterofunctionalization of Aryl Cyclopropanes

5 Photoredox-Catalyzed Fluoroallylation of gem-Difluorocyclopropanes

6 Conclusion

Key words

arylcyclopropanes - photoredox catalysis - single-electron transfer - radical cation - S_N2 reaction

Publication History

Received: 16 November 2022

Accepted after revision: 09 December 2022

Accepted Manuscript online:
09 December 2022

Article published online:
05 January 2023

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