Generation and Reactions of ε-Carbonyl Cations via Group 13 Catalysis

Abstract

The generation of ε-carbonyl cations and their reactions with nucleophiles is accomplished readily without transition metal cation stabilization, using the ε-bromide dienoate or dienone starting materials and GaCl3 or InCl3 catalysis. Arene nucleophiles are somewhat more straightforward than allyltrimethylsilane, but allyltrimethylsilane and propiophenone trimethysilyl enol ether each react successfully with InCl3 catalysis. The viability of these cations is supported by DFT calculations.

Keywords

• ε-carbonyl cations
• catalysis
• umpolung
• electrophilic aromatic substitution
• allylation