50 years of superbases made from organolithium compounds and heavier alkali metal alkoxides

• Authors: Lubomír Lochmann , Miroslav Janata
• Languages of publication: EN

Abstracts

EN

A review of reactions of organolithium compounds (RLi) with alkali metal alkoxides is presented. On the one hand, simple lithium alkoxides form adducts with RLi the reactivity of which differs only slightly from that of RLi. On the other hand, after mixing heavier alkali metal alkoxides (R’OM, M = Na, K, Rb, Cs) with RLi, a new system is formed, which has reactivity that dramatically exceeds that of the parent RLi. A metal interchange, according to the equation RLi + R’OM = RM + R’OLi, occurs in this system, giving rise to a superbase. This reaction is frequently used for the preparation of heavier alkali metal organometallic compounds. Similar metal interchange takes place between R’OM and compounds such as lithium amides and lithium enolates of ketones or esters, thus demonstrating the general nature of this procedure. Superbases react easily with many types of organic compounds (substrates), resulting in the formation of a heavier alkali metal derivative of the substrate (metalation). The metalated substrate can react in situ with an electrophile to yield the substituted substrate, a procedure that is frequently used in synthetic and polymer chemistry. An improved mechanism of metal interchange and reaction of superbases with substrates is proposed.

Keywords

EN

Superbases; Heavier alkali metal compounds; Lithium-heavier alkali metal interchange; Metalation

• Publisher: De Gruyter Open
• Journal: Open Chemistry
• Year: 2014
• Volume: 12
• Issue: 5
• Pages: 537-548

Dates

published

1 - 5 - 2014

online

21 - 2 - 2014

Contributors

author

Lubomír Lochmann

• Institute of Macromolecular Chemistry of Academy of Sciences of the Czech Republic

author

Miroslav Janata

• Institute of Macromolecular Chemistry of Academy of Sciences of the Czech Republic

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Identifiers

DOI

10.2478/s11532-014-0528-0