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The use of gem‐difluorinated cyclopropanes (gem‐DFCPs) as fluoroallyl surrogates under transition‐metal catalysis has drawn considerable attention recently but such reactions are restricted to producing achiral or racemic mono‐fluoroalkenes. Herein, we report the first enantioselective allylation of indoles under rhodium catalysis with gem‐DFCPs. This reaction shows exceptional branched regioselectivity towards rhodium catalysis with gem‐DFCPs, which provides an efficient route to enantioenriched fluoroallylated indoles with wide substrate scope and good functional group tolerance. [ABSTRACT FROM AUTHOR]

As a special class of cyclopropanes, gem -difluorinated cyclopropanes have many fascinating properties as a result of the gem -difluoro substitution; thus, their reactions have received much attention from the synthetic chemistry community. Recently, gem -difluorinated cyclopropanes have gradually emerged as a type of novel and unique fluorinated allylic synthon in cross-coupling reactions for the synthesis of monofluoroalkenes. Herein, we briefly summarize recent advances in transition-metal-catalyzed reactions of gem -difluorinated cyclopropanes. 1 Introduction 2 Palladium-Catalyzed Reactions with Linear Selectivity 3 Palladium-Catalyzed Reactions with Branched Selectivity 4 Other Metal-Catalyzed Reactions 5 Conclusions [ABSTRACT FROM AUTHOR]

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 [ABSTRACT FROM AUTHOR]

Herein, we report a rhodium catalyzed directing‐group free regioselective C−H allylation of simple arenes. Readily available gem‐difluorinated cyclopropanes can be employed as highly reactive allyl surrogates via a sequence of C−C and C−F bond activation, providing allyl arene derivatives in good yields with high regioselectivity under mild conditions. The robust methodology enables facile late‐stage functionalization of complex bioactive molecules. The high efficiency of this reaction is also demonstrated by the high turnover number (TON, up to 1700) of the rhodium catalyst on gram‐scale experiments. Preliminary success on kinetic resolution of this transformation is achieved, providing a promising access to enantio‐enriched gem‐difluorinated cyclopropanes. [ABSTRACT FROM AUTHOR]

Direct synthesis of gem-difluorinated carbocyclic molecules represents a longstanding challenge in organic chemistry. Herein, a Rh-catalyzed [3+2] cycloaddition reaction between readily available gem-difluorinated cyclopropanes (gem-DFCPs) and internal olefins has been developed, enabling the efficient synthesis of gem-difluorinated cyclopentanes with good functional group compatibility, excellent regioselectivity and good diastereoselectivity. The resulting gem-difluorinated products can undergo downstream transformations to access various mono-fluorinated cyclopentenes and cyclopentanes. This reaction demonstrates the use of gem-DFCPs as a type of "CF 2 " C3 synthon for cycloaddition under transition metal catalysis, which provides potential strategy for synthesizing other gem-difluorinated carbocyclic molecules., (© 2023 Wiley-VCH GmbH.)

Herein, we report a rhodium catalyzed directing-group free regioselective C-H allylation of simple arenes. Readily available gem-difluorinated cyclopropanes can be employed as highly reactive allyl surrogates via a sequence of C-C and C-F bond activation, providing allyl arene derivatives in good yields with high regioselectivity under mild conditions. The robust methodology enables facile late-stage functionalization of complex bioactive molecules. The high efficiency of this reaction is also demonstrated by the high turnover number (TON, up to 1700) of the rhodium catalyst on gram-scale experiments. Preliminary success on kinetic resolution of this transformation is achieved, providing a promising access to enantio-enriched gem-difluorinated cyclopropanes., (© 2021 Wiley-VCH GmbH.)