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  • Title: Stabilization of ketone and aldehyde enols by formation of hydrogen bonds to phosphazene enolates and their aldol products.
    Author: Kolonko KJ, Reich HJ.
    Journal: J Am Chem Soc; 2008 Jul 30; 130(30):9668-9. PubMed ID: 18593122.
    Abstract:
    Solution properties of enolates generated using the phosphazene (Schwesinger) base P4-tBu were investigated by NMR spectroscopy. With a full equivalent of base the benzyl ketones 1a and 1b, the acetophenone 2, the arylacetaldehyde 1c, and the methyl arylacetate 1d formed the expected "naked" (P4H+) enolates 3 and 7. However, at a half-equivalent of base the ketones 1a and 1b as well as the aldehyde 1c formed solutions of stable hydrogen-bonded dimeric (enol-enolate) structures (4). The acetophenone 2, on the other hand, forms only traces of the H-bonded dimer 8 during deprotonation of 2. The thermodynamic product was the isomeric self-aldol condensation product 12. The mechanism of this condensation was elucidated by low temperature rapid-injection (RI) NMR spectroscopy. Solutions of 8 stable enough for NMR characterization could be transiently generated by semiprotonation of the enolate 7 with HCl.OEt2 at -130 degrees C using RINMR. The ester enolate 1d gave no trace of 4d even on a time scale as short as a few seconds at -130 degrees C either during the semideprotonation of 1d, or during semiprotonation of the enolate 3d. Long-lived solutions of the enols derived from 1a, 1b, 1c, and 2 (but not 1d) could be produced by full protonation of the phosphazene enolates with HCl.OEt2 at low temperature.
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