Reduction of Strained Polycycles: How Much Strain Can a Pyrene Anion Take?
| Autor: | Mordecai Rabinovitz, James J. Fleming, Michael R. Mannion, Greg P Manning, Brad L Merner, Ivan Aprahamian, Rudolf J. Vermeij, Tuvia Sheradsky, Graham J. Bodwell |
|---|---|
| Rok vydání: | 2004 |
| Předmět: |
Steric effects
Reaction mechanism Intramolecular reaction Stereochemistry chemistry.chemical_element General Chemistry Biochemistry Medicinal chemistry Catalysis Solvent Metal chemistry.chemical_compound Colloid and Surface Chemistry chemistry Intramolecular force visual_art visual_art.visual_art_medium Pyrene Lithium |
| Zdroj: | Journal of the American Chemical Society. 126:6765-6775 |
| ISSN: | 1520-5126 0002-7863 |
| DOI: | 10.1021/ja040039u |
| Popis: | The reduction of a series of [n](2,7)pyrenophanes (n = 7-10) with lithium or potassium metal shows that the strain in the system, controlled by the length of the tether, determines the nature of the reduction products. The reduction of [7](2,7)pyrenophane (2) and [2]metacyclo[2](2,7)pyrenophane (3) leads to reductive dimerization followed by novel intramolecular sigma-bond formation as a means of escaping strained anti-aromaticity. [8](2,7)Pyrenophane (4) affords only reductive dimerization, and no two-electron reduction is observed. The reduction of [9](2,7) pyrenophane (5) and [10](2,7)pyrenophane (6) leads to reductive dimerization, followed by the formation of a dianionic anti-aromatic species, which eventually cleaves the solvent, THF-d(8). The similarity between the reduction of the latter systems and the reduction of pyrene (1) is discussed. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|