ChemInform Abstract: Reaction of Organolithium Compounds with Alkali Metal Alkoxides - A Route to Superbases

ChemInform ◽  
2000 ◽  
Vol 31 (50) ◽  
pp. no-no
Author(s):  
Lubomir Lochmann
Keyword(s):  
Alkali Metal ◽  
Metal Alkoxides ◽  
Organolithium Compounds

Lithium - Heavier alkali metal exchange in organolithium compounds induced by alkoxides of heavier alkali metals and reactions occurring in this system

1988 ◽  
Vol 53 (1) ◽  
pp. 76-96 ◽  
Author(s):  
Lubomír Lochmann ◽  
Jiří Trekoval
Keyword(s):  
Alkali Metal ◽  
Exchange Reaction ◽  
Alkali Metals ◽  
Metal Exchange ◽  
Metal Alkoxides ◽  
Individual State ◽  
Organolithium Compounds ◽  
Reactive Compound ◽  
The Individual ◽  
Derivatives Of

Organolithium compounds of various types undergo an exchange reaction lithium-heavier alkali metal when treated with heavier alkali metal alkoxides. In the presence of a third reactive compound the exchange reaction gives rise to a compound of the third component substituted with the heavier alkali metal. Using this exchange reaction, organic derivatives of heavier alkali metals in the individual state can be easily prepared. The mechanism of such reactions is discussed, and the formation of lithium alkoxide is assumed to contribute significantly to the driving force of the reaction. Organic compounds of heavier alkali metals possess a considerably higher reactivity than organolithium compounds, and are therefore used as reactive intermediates in preparative chemistry, or as polymerization initiators in macromolecular chemistry. This review provides information about the scope and possibilities of this exchange reaction, which has been increasingly widely used in the recent years.

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

2014 ◽  
Vol 12 (5) ◽  
pp. 537-548 ◽  
Author(s):  
Lubomír Lochmann ◽  
Miroslav Janata
Keyword(s):  
Alkali Metal ◽  
Organometallic Compounds ◽  
General Nature ◽  
Metal Alkoxides ◽  
Organolithium Compounds ◽  
Lithium Amides ◽  
Lithium Enolates ◽  
Metal Derivative ◽  
The One

AbstractA 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.

(Alk-1-ynyl)oxiranes in the Reaction of (Alk-1-ynyl)chlorocarbenes with Alkali Metal Alkoxides

1995 ◽  
Vol 5 (5) ◽  
pp. 181-182 ◽  
Author(s):  
Konstantin N. Shavrin ◽  
Valentin D. Gvozdev ◽  
Oleg M. Nefedov
Keyword(s):  
Alkali Metal ◽  
Metal Alkoxides

ChemInform Abstract: Asymmetric Alkylation Catalyzed by Chiral Alkali Metal Alkoxides of TADDOL. Synthesis of α-Methyl Amino Acids.

ChemInform ◽  
2010 ◽  
Vol 30 (50) ◽  
pp. no-no
Author(s):  
Yu. N. Belokon ◽  
K. A. Kochetkov ◽  
T. D. Churkina ◽  
N. S. Ikonnikov ◽  
A. A. Chesnokov ◽  
...  
Keyword(s):  
Amino Acids ◽  
Alkali Metal ◽  
Metal Alkoxides ◽  
Asymmetric Alkylation
Sign in / Sign up

Export Citation Format

Share Document