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DOI: 10.1055/a-1536-2738
Rhodium-Catalyzed Direct Allylation of Simple Arenes by Using Gem-Difluorinated Cyclopropanes as Allyl Surrogates
Start-up funding from Sichuan University (YJ201965), National Natural Science Foundation of China (22001180), Thousand Young Talents Program of China (15-YINGXIA).
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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 - arenesPublikationsverlauf
Eingereicht: 09. Juni 2021
Angenommen nach Revision: 24. Juni 2021
Accepted Manuscript online:
24. Juni 2021
Artikel online veröffentlicht:
15. Juli 2021
© 2021. Thieme. All rights reserved
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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.
For selected examples, see:
For selected examples of cross-coupling reactions between aryl and allyl fragments, see:
For selected examples of transition-metal-catalyzed ortho-allylations, see:
For selected examples of transition-metal-catalyzed meta-allylations, see:
For selected reviews, see: