Halide Anion Triggered Reactions of Michael Acceptors with Tropylium Ion.

Abstract

Tropylium bromide undergoes noncatalyzed, regioselective additions to a large variety of Michael acceptors. In this way, acrylic esters are converted into β-bromo-α-cycloheptatrienylpropionic esters. The reactions are interpreted as nucleophilic attack of bromide ions at the electron-deficient olefins and the approach of the tropylium ion to the incipient carbanion. Quantum chemical calculations were performed to elucidate the analogy to the amine- or phosphine-catalyzed Rauhut-Currier reactions. Subsequent synthetic transformations of the bromo-cycloheptatrienylated adducts are reported.