KNORR, R and FERCHLAND, K and MEHLSTAUBL, J and HOANG, TP and BOHRER, P and LUDEMANN, HD and LANG, E (1992) (E,Z) EQUILIBRIA .15. SYNTHESES AND LABILITY OF THE CONFIGURATION OF 2-IMINOINDAN DERIVATIVES WITH FRONT STRAIN. CHEMISCHE BERICHTE-RECUEIL, 125 (9). pp. 2041-2049. ISSN 0009-2940,
Full text not available from this repository.Abstract
Syntheses and properties are described for sterically shielded imines R2C = NR (3c, e, g - k), which are rather inert toward nucleophiles. Nucleophilic attack at the nitrogen atom of 3k is indicated by the formation of the azine 4. (E,Z) Configurational diastereotopomerization (anti/syn) is strongly dependent on N substituents [CH3, Phenyl, 1-naphthyl, acetyl, Si(CH3)3, cyano, SC6H5, SOC6H5, SO2C6H5, and nitro]. It is accelerated by front strain along the C=N bond in 3a - c, e, g, h, j, and k and provides an energetic basis (by DELTAG(not-equal) and DELTADELTAG(not-equal) values) for the gauging of force-field parameters. This (E,Z) stereo-mutation is characterized by a vanishing solvent dependence and a positive volume of activation (+ 10.2 cm3 mol-1 for 3a). In contrast to other pi acceptor substituents, the N-nitro group in 31 retards (E,Z) interconversion.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | QUANTUM-MECHANICAL CALCULATIONS; N-METHYLENECARBOXAMIDES; DYNAMIC STEREOCHEMISTRY; NITROGEN INVERSION; CRYSTAL-STRUCTURE; REACTION VOLUMES; DOUBLE-BOND; IMINES; ISOMERIZATION; RESONANCE; BASICITY; DIASTEREOTOPOMERIZATION, (E/Z); IMINES; STERIC SHIELDING; STERIC STRAIN |
| Depositing User: | Dr. Gernot Deinzer |
| Last Modified: | 19 Oct 2022 08:44 |
| URI: | https://pred.uni-regensburg.de/id/eprint/54400 |
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