Mesomeric stabilization compounds

Benzyl-type carbanions and their metallo compounds, derived from aromatic or hetero-aromatic precursors, bearing carbon- or hetero-substituents, are readily available with variable substitution patterns due to their mesomeric stabilization (see Section 1.3.2.2)2. Even dicarbanions are accessible without difficulty3,4. The equilibrium acidities of many aromatic hydrocarbons have been determined5-7. The acidities of a-hetero-substituted toluenes8 are similar to those of the corresponding allylic compounds and can usually be generated by the same methods. 

If the mesomeric stabilization is provided by a double bond, the lithiated species is a homoenolate synthon, as shown in Scheme 44a. Reaction with an electrophile typically occurs at the y-position, yielding an enamine, which can then be hydrolyzed to a carbonyl compound. An important application of this approach is to incorporate a chiral auxiliary into the nitrogen substituents so as to effect an asymmetric synthesis. 2-AzaaUyl anions (Scheme 44b), which are generated by tin-lithium exchange, can be useful reagents for inter- and intramolecular cycloaddition reactions. ... 

II. NON-MESOMERICALLY STABILIZED ORGANOLITHIUM COMPOUNDS A. Acidification by Dipole Stabilization... 

Benzylic compounds have—compared to the corresponding methyl derivatives—a higher thermodynamic acidity by 10 to 15 pATa units . Mesomeric stabilization requires a considerable flattening of the carbanionic centre towards sp hybridization (the sum of bond angles is 360° for sp and 328° for sp ). However, we should be aware that even if the carbanionic framework would be completely planar, the ion pair 209 is a planar-chiral species. For epimerization, the cation has to migrate from one face to the other one (equation 48). Due to a more facile flipping of the carbanionic centre and an easier formation of solvent-separated ion pairs, most of chiral benzyUithium compounds 208/ewi-208 racemize with great ease. 

Allylic compounds have acidities similar to those of the corresponding benzylic analogues . Due to the mesomeric stabilization, the carbanionic centre is considerably... 

Fluorine in organic compounds is associated with a set of electronic effects inductive and mesomeric, stabilizing and destabilizing, pulling or pushing electrons, which are convincingly... 

The UV spectra of simple pyrrolopyridines have a typical aromatic appearance with several shoulders in addition to the main peaks shown in Table 2. The compounds are with one exception stronger bases than pyridine (pfsTa 5.2), suggesting mesomeric stabilization of the cation (Scheme 3). This is confirmed by the bathochromic shift of band III on protonation. 

Nitrene generation from nitroso and nitro compounds with triethyl phosphite can also be used. For example, (304 R = NO) and TEP give (305) in 98% yield (63JCS42). The pyrrole (309) and TEP, refluxed in xylene (7 d), give the mesomerically stabilized heteropen-talene derivative (310) which undergoes cycloaddition reactions (Scheme 91) (79JOC622). 

Benzyl-type organolithium compoimds are stabilized by the mesomeric interaction of the negative charge of the carbanionic center with the aromatic n-system. The thermodynamic acidity of the benzylic compounds is 10 to 15 pK units higher than of the corresponding methyl derivatives [127]. Mesomeric stabilization requires a considerable flattening of the carbanionic center towards sp -hy-bridization [128]. As a consequence, the configurational stability is decreased, and - with few exceptions - most of the benzyllithium derivatives suffer from rapid racemization [Eq. (56)],see Sect. 3.2. 

The best-known equation of the type mentioned is, of course, Hammett s equation. It correlates, with considerable precision, rate and equilibrium constants for a large number of reactions occurring in the side chains of m- and p-substituted aromatic compounds, but fails badly for electrophilic substitution into the aromatic ring (except at wi-positions) and for certain reactions in side chains in which there is considerable mesomeric interaction between the side chain and the ring during the course of reaction. This failure arises because Hammett s original model reaction (the ionization of substituted benzoic acids) does not take account of the direct resonance interactions between a substituent and the site of reaction. This sort of interaction in the electrophilic substitutions of anisole is depicted in the following resonance structures, which show the transition state to be stabilized by direct resonance with the substituent ... 

Combination of the hydroxyl ion with the mesomeric cation involves the removal of a double bond. For the quaternary pyridinium compounds this causes the total loss of the aromaticity. For quaternary quinolinium and isoquinolinium compounds, the aromatic character of one of the two rings is lost, and for the quaternary acridinium compounds that of one out of three. Hence., the order of stabilities of these compounds (determined by Hantzsch ) is explained. - Comparison of quaternary 3,4-dihydroisoquinolinium compounds and their isoquinolinium analogs with respect to the equilibrium (5) (4) shows that a much higher hydroxyl ion concentration is necessary for the isoquinolinium ions to form the carbinolamine. This is because the transition from the quaternary 3,4-dihydroisoquinolinium ions into the undissociated carbinolamine involves significantly smaller loss of mesomeric energy than that for the quaternary isoquinolinium hydroxides. ... 

Pfleiderer has suggested that the 7-hydroxy group exists as such in these compounds because this form is stabilized by mesomerism of type 191 (R — H). The tautomerism of 7-hydroxypteridine-2,4-dione in the excited electronic state has been studied on the basis of its fluorescence spectrum. 

The fact that the equilibrium for aminopyridine 1-oxides is displaced further in favor of the amino form than is the equilibrium for aminopyridines is in accord with the mesomerism of these compounds. The stabilization of the amino forms (e.g., 241) by structures of type 240 is more effective than the corresponding stabilization in the pyridine series since the negative charge is associated with the oxygen atom. The stabilization of the imino form (e.g., 242) by structures of type 243 is less than in the pyridine series because of the adverse inductive effect of the oxygen atom. ... 

Coupling to both termini of the 2-methyl-2-propcnyl residue occurs when the complex 5, formed from the iodo compound 4 and stiver tetratluoroborate, is allowed to react with an excess of aldehyde, giving rise to diastcreomerically pure 4-fluoro-2,4,6-trisubstituted tetrahy-dropyrans 617. The details of the reaction and, as well, the origin of stereoselectivity is unclear at present. It would not be surprising if the reaction is restricted to those aldehydes leading in the first step to homoallylic alcohols capable of forming mesomerically highly stabilized carb-enium ions on solvolysis. 

Although the reaction mechanism of this type of reactions is not fully elucidated, it is easily anticipated that no intramolecular special stabilization effect for the carbanion generated from decarboxylation is expected, different from the case of malonic acid-type compounds. Moreover, cinnamic acid derivatives that have both the electron-donating and withdrawing substituents have been reported to undergo this reaction. This fact suggests that the enzyme itself stabilizes the transition state without the aid of mesomeric and inductive effects of the other part of the substrate molecule itself. If such unknown mechanism also works for other... 

The reactions and compound presented in this chapter support the notion that the formation of o-QMs from the parent phenols is a quite complex process. In the case of the oxidation by Ag20 but also likely in other oxidations, a zwitterionic intermediate is involved that can be stabilized intermolecularly, for example, by electrostatic interaction with other suitable zwitterions, or intramolecularly by neighboring groups or inductive/mesomeric effects. By stabilizing the zwitterionic intermediate and destabilizing the o-QM, the energetic gap between these two intermediates is lowered and... 

Huckel s 4n+2 //-electron rule is a necessary but not a sufficient condition for aromaticity. Coplanarity and electronegativity restrictions of constituent atoms represent the most important restrictions. Phos-phole is a marginally aromatic five-membered heterocycle76 (see further examples and discussion). Mesoionic compounds, mesomeric betaines, and 2H-and 4i+-pyrone have all been considered to be weakly aromatic or non-aromatic, though their conjugated acids are aromatic. Spectroscopic data evidenced the aromaticity of dioxolium and oxathiolium cations 59 (Scheme 28) and mesoionic oxathioles not in the classical sense but by their ring currents and chemical stability.77... 

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