Toward improving the chemistry of N-acyliminium ions: nucleophilic substitution reactions of pyrrolidinone derivatives with trialkylsilyl nucleophiles catalyzed by triisopropylsilyltrifluoromethane sulfonate (TIPSOTf).

[reaction: see text] Nucleophilic substitution reactions of racemic and chiral 5-acetoxy-, 5-ethoxy-, and 5-methoxypyrrolidin-2-ones by silicon-based nucleophiles were efficiently catalyzed by TIPSOTf. This process was found to be general and accommodates a broad range of substrate-nucleophile combinations.