Relative ease of carbanion formation

It has been found that there is often a correlation between the rate of deprotonation (kinetic acidity) and the thermodynamic stability of the carbanion (thermodynamic acidity). Because of this relationship, kinetic measurements can be used to construct orders of hydrocarbon acidities. These kinetic measurements have the advantage of not requiring the presence of a measurable concentration of the carbanion at any time instead, the relative ease of carbanion formation is judged from the rate at which exchange occurs. This method is therefore applicable to very weak acids, for which no suitable base will generate a measurable carbanion concentration. 

Simple sulfonyl carbanions which do not contain additional carbanion-stabilising groups, e.g. carbonyl groups or heteroatoms, can be readily alkylated in high yield by modern techniques with the use of alkyllithiums and lithium amide bases. A number of allylic halides have been successfully used. In allylic halides, the halogen directly attached to the double-bonded carbon is relatively inert towards nucleophilic attack (Scheme 41). In this way, sulfones (96) can be transformed via desulfonation into vinyl halides (97) or into ketones (98) by hydrolysis (Scheme 41). In contrast to ordinary alkyl sulfones, triflones (99) can be alkylated under mildly basic conditions (potassium carbonate in boiling acetonitrile) (Scheme 42). The ease of carbanion formation from triflones (99) arises from the additional electron-withdrawing (-1) effect of the trifluoromethyl moiety. 

The relative ease of pinacolization is primarily determined by the reduction potential of the carbonyl group involved. Many reductants are therefore selective for aromatic and other electronically activate systems. Moreover, as a result of this ready reduction, pinacolization of such carbonyls can be effected by either anionic or radical routes. For example, treatment of aromatic aldehydes or ketones with Mg/TMSCl in HMPA promotes pinacolization via formation of an a-silyloxy carbanion - and nucleophilic attack on a second carbonyl group (equation 2). Furthermore, with benzaldehyde the reaction is stereodirecting with a preference for /it-coupling. Whilst an alternate coupling metht using the milder... 

Aldol-type condensation of an aromatic aldehyde with activated methylarene or phenylacetic acid is a useful reaction for preparing stilbene derivatives. Starting from para-substituted toluenes or para-substituted aromatic aldehydes, one can obtain 4,4 -disubstituted stilbenes. This reaction is relatively simple but has low yield. As an example, condensation of 2,4-dinitrotoluene and 4-nitrophenylacetic acid with aromatic aldehyde was studied [26]. The reaction involves carbanion addition to the carbonyl group. The carbanion is formed by the extraction of proton from the active methylene group of 2,4-dinitrotoluene by the base (usually, piperidine). The carbanion then adds to carbon atoms of the carbonyl group of the aldehyde. The reaction will therefore be facilitated by the ease of both the formation of the... 

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