Chemistry of Stable α-Halogenoorganolithium Compounds and the Mechanism of Carbenoid Reactions

Some years ago we found that α-halogenoorganolithium compounds (carbenoids) previously postulated as transient intermediates in organolithium-initiated α-eliminations can be obtained in a stable form. The present paper is a review of the methods for their preparation and of their reactivity. They possess both nucleophilic and electrophilic properties, which can be utilized singly or combained for the synthesis of substances of very different types. Their thermolability, which is considerably reduced (with only one known exception) by the solvent tetrahydrofuran, is due to electrophilic secondary reactions, in which carbenes evidently do not occur as intermediates. A mechanism is proposed which fits the experimental data for various carbenoid reactions.