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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]

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 "CF2" C3 synthon for cycloaddition under transition metal catalysis, which provides potential strategy for synthesizing other gem‐difluorinated carbocyclic molecules. [ABSTRACT FROM AUTHOR]