Alkali metal enolates and cryptands - a novel type of strong base

Pierre, J.-L.; Goaller, R. Le; Handel, Henri

doi:10.1021/ja00493a048

Cited by 10 publications

(3 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Since and l3C(sp2) chemical shift values for conjugated systems have profound correlation with electron density of the atoms,10 the observed chemical shift changes should result mainly from delocalization of a negative charge. 11 The ab initio MO calculations with STO-3G minimal basis set were carried out on the model enol 9 and enolate 10, and the electron distribution obtained is given in Figure 3.12•13 The result indicates that, in going from 9 to 10, all of the protons increase the electron density. Likewise electron densities of the vinyl, ortho, meta, and para carbons enhance by the charge delocalization.…”

Section: Trisidialkylaminoisulfonium Enolatesmentioning

confidence: 99%

Tris(dialkylamino)sulfonium enolates

Noyori¹,

Nishida²,

Sakata³

et al. 1980

J. Am. Chem. Soc.

117

View full text Add to dashboard Cite

Section: Trisidialkylaminoisulfonium Enolatesmentioning

confidence: 99%

Tris(dialkylamino)sulfonium enolates

Noyori¹,

Nishida²,

Sakata³

et al. 1980

J. Am. Chem. Soc.

117

View full text Add to dashboard Cite

“…and the residue recrystallized twice from acetone or acetonitrile. 11 338.0 mg of 5, 440.0 mg of 3 and 408.0 mg of II (2.0 mmol in each case) are heated to boiling for 6 h in acetonitrile. No precipitation occurs.…”

Section: Substitution Products 8-10mentioning

confidence: 99%

Crown Ether Assisted Chemical Reactions, II. Crown Ether Complexes of Potassium Phthalimide, Sodium Saccharinate and Sodium Acetylacetonate: New Reagents Containing Activated Anions

Raßhofer

Oepen

Vögtle

1979

Israel Journal of Chemistry

View full text Add to dashboard Cite

The synthesis of several crown ether and cryptand complexes with potassium phthalimide, sodium saccharinate and sodium acetylacetonate is reported. The anions in the complexes prove to be activated; this has been used to carry out a series of new nucleophilic substitutions with 2,4‐dinitrochlorobenzene, pentachloropyridine and pentafluoropyridine. Without addition of crown ethers these reactions could not be achieved. Only pentafluoropyridine reacts with potassium phthalimide alone, yielding a monosubstituted product. With crown ether assistance threefold substitution could be realized with pentafluoropyridine, whereas pentachloropyridine gave only monosubstitution.

show abstract

“…Therefore, enolate anions have found many applications in synthetic chemistry. Reactions of metal carbonyls with enolates 2) , and activation of enolates by complexation with a cryptand 3) were recently published. On the other hand it turned out that enolate anions can act as intermediates in the anionic polymerization of some lactones initiated by potassium tert-butoxide 4) .…”

Section: Introductionmentioning

confidence: 99%