The synthesis of 3‐(1′,1′‐difluoroalkyl)‐3‐hydroxyindolin‐2‐ones by employing α,α‐difluoro‐α‐phenylsulfanyl‐α‐trimethylsilylmethane (PhSCF2SiMe3) as a gem‐difluoromethylene building block is described. The reaction involves a fluoride‐catalyzed nucleophilic addition of PhSCF2SiMe3 to various isatin derivatives followed by the reductive cleavage of the phenylsulfanyl group to lead to 3‐(difluoromethyl)‐3‐hydroxyindolin‐2‐ones in good yields. Under similar reduction conditions but in the presence of activated olefins, an intermolecular radical trapping reaction took place to yield 3‐(1′,1′‐difluoroalkyl)‐3‐hydroxyindolin‐2‐one derivatives.

A convenient and efficient synthetic strategy to prepare enantioenriched gem-difluoromethylenated spiro-pyrrolidinyl and spiro-piperidinyl oxindoles is described. Fluoride-mediated diastereoselective nucleophilic addition of PhSCF2SiMe3 to chiral N-tert-butanesulfinyl ketimines derived from isatins was a key step and provided diastereomeric adducts, which were readily separable. Removal of the chiral sulfinyl group followed by structural manipulation afforded chiral gem-difluoromethylenated spiro-pyrrolidinyl and spiro-piperidinyl oxindoles.

The Front Cover shows the synthesis of 3‐(1',1'‐difluoroalkyl)‐3‐hydroxyindolin‐2‐ones by employing α,α‐difluoro‐α‐phenylsulfanyl‐α‐trimethylsilylmethane (PhSCF2SiMe3) as a gem‐difluoromethylene building block. The reaction involves a fluoride‐catalyzed nucleophilic addition of PhSCF2SiMe3 to isatin derivatives followed by reductive cleavage of the phenylsulfanyl group leading to 3‐(difluoromethyl)‐3‐hydroxyindolin‐2‐ones in good yields. Under similar reduction conditions, in the presence of activated olefins, an intermolecular radical trapping reaction takes place to yield 3‐(1',1'‐difluoroalkyl)‐3‐hydroxyindolin‐2‐ones. The present work provides a general approach to 3‐(1',1'‐difluoroalkyl)‐3‐hydroxyindolin‐2‐one frameworks, which could have particular significance in organic synthesis and pharmaceutical applications. More information can be found in the https://doi.org/10.1002/ejoc.201701106