Organolithium Reagent - Reactivity

Reactivity

Some general reactions of organolithium compounds are:

• Protonation in reaction with any compound containing acidic protons
• Reaction with ketones and aldehydes to alcohols.
• Reaction with epoxides to alcohols.
• Reaction with carboxylic acid salts and acid chlorides to the corresponding ketone.
• Reaction with carboxylic esters to give tertiary alcohols. In the example shown, ethyllithium was shown to be very effective, but ethylmagnesium bromide gave mainly reduction products.

• Reaction with oximes to the corresponding amines.
• Reaction with isonitriles to the corresponding lithium aldimine. Subsequent hydrolysis effectively converts the organolithium compound to its aldehyde.
• Reaction with certain epoxides to the corresponding alkenes.

Organolithium reagents also react with the ether solvents that are used for most reactions. The table below list approximate half-lives of several of the more common lithium reagents in typical solvents: