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2014 | 12 | 5 | 537-548
Article title

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

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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.
Publisher

Journal
Year
Volume
12
Issue
5
Pages
537-548
Physical description
Dates
published
1 - 5 - 2014
online
21 - 2 - 2014
Contributors
  • Institute of Macromolecular Chemistry of Academy of Sciences of the Czech Republic, janata@imc.cas.cz
  • Institute of Macromolecular Chemistry of Academy of Sciences of the Czech Republic, l.lochmann@volny.cz
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Publication order reference
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YADDA identifier
bwmeta1.element.-psjd-doi-10_2478_s11532-014-0528-0
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