Rhodium-Catalyzed Direct Allylation of Simple Arenes by Using Gem-Difluorinated Cyclopropanes as Allyl Surrogates

Abstract

Gem-difluorinated cyclopropanes have become an important type of allyl surrogate in transition-metal-catalyzed ring-opening processes, as demonstrated recently through various important advances, especially with palladium catalysis. The versatile fluorinated allyl species generated in this way from gem-difluorinated cyclopropanes exhibit unique advantages compared with conventional allyl sources. By using gem-difluorinated cyclopropanes as allyl surrogates, we achieved a direct allylation of simple arenes through rhodium catalysis under mild conditions. This transformation permits directing-group-free allylation of simple arenes, including electron-neutral, electron-rich, and electron-deficient ones. Here, we give a brief introduction to this area and we discuss our thoughts regarding our recent work and its design.

1 Introduction

2 Our Design

3 Condition Optimization and Substrate Scope

4 Applications in Synthesis

5 Mechanistic Discussions

6 Conclusion and Outlook

Key words

difluorocyclopropanes - transition-metal catalysis - allylation - C–C bond activation - rhodium catalysis - arenes

Publication History

Received: 09 June 2021

Accepted after revision: 24 June 2021

Accepted Manuscript online:
24 June 2021

Article published online:
15 July 2021

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• 26 This conclusion is also supported by the following two facts. (1) Our reaction is base-free and a release of HF is observed in the reaction, demonstrating that the reaction proceeds under acidic conditions. In comparison, CMD-type C–H activation processes usually occur under basic conditions. (2) Electron-rich arenes are more active, giving the allylated products at ambient temperatures, whereas electron-deficient arenes require elevated temperatures.