Metalloaldimines are acyl anion equivalents derived from isonitriles and organometallic reagents. Significant advances have been achieved in the use of lithium aldimines as synthetic intermediates. Lithium aldimines couple with aryl, vinyl, and acetylenic halides. These coupling reactions are unparalleled by other acyl anion equivalents. Lithium aldimines are added to enolizable aldehydes by using an inverse addition technique. In that reaction with aldehydes, the (alpha)-hydroxyimine products undergo a novel tautomerization to give exclusively (alpha)-amino ketones. The major disadvantage of lithium aldimines as synthetic intermediates is their high basicity. / Non-alkali metalloaldimines, such as magnesium, copper, aluminum and cadmium aldimines, are uncharacteristically stable toward electrophiles. ('13)C NMR spectroscopy studies show that magnesium aldimines have no effective charge on the aldimine carbon. This data supports a dimeric structure for the non-alkali metalloaldimines which accounts for the absence of an effective charge on the aldimine carbon and thus for their unreactivity. / Certain aryl imines prepared from lithium aldimines and aryl halides display unusual NMR spectra. These spectra indicate that these imines have a very slow carbon-nitrogen single bond rotation resulting in slow chemical exchange. This process allows the observation of magnetically nonequivalent conformers in the NMR spectra. / Source: Dissertation Abstracts International, Volume: 42-06, Section: B, page: 2378. / Thesis (Ph.D.)--The Florida State University, 1981.
| Identifer | oai:union.ndltd.org:fsu.edu/oai:fsu.digital.flvc.org:fsu_74570 |
| Contributors | MARKS, MAURICE JOEL., Florida State University |
| Source Sets | Florida State University |
| Detected Language | English |
| Type | Text |
| Format | 124 p. |
| Rights | On campus use only. |
| Relation | Dissertation Abstracts International |
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