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Synthetic Communications
An International Journal for Rapid Communication of Synthetic Organic Chemistry
Volume 29, 1999 - Issue 24
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Original Articles

Oxidation of Enolate Anion by Hypervalent Iodine Compounds: Synthesis of α-Tempo Carbonyl Compound, A New Living Radical Polymerization Initiator

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Pages 4361-4366 | Received 22 Feb 1999, Published online: 25 Sep 2007

References

  • Paquette, L. A., 1995. Encyclopedia of Reagents for Organic Synthesis. Vol. Vol. 7. Chichester: John Wiley & Sons; 1995. pp. 175–198.
  • Hawker, C. J., 1997. Acc. Chem. Res. 30 (1997), pp. 373–382, and references cited therein.
  • Hawker, C. J., Barclay, G. G., Orellana, A., Dao, J., and Devonport, W., 1996. Macromolecules 29 (1996), pp. 5245–5254.
  • Braslau, R., Burrill, L. C., Siano, M., Naik, N., Howden, R. K., and Mahal, L. K., 1997. Macromolecules 30 (1997), pp. 6445–6450.
  • Kim, J. W., Lee, J. -J., Lee, S. -H., and Ahn, K. -H., 1998. Synth. Commun. 28 (1998), pp. 1287–1292.
  • , Typically, in a 50 mL round bottomed flask, ethyl phenylacetate (200 mg, 1.22 mmol) was dissolved in 6 mL THF under nitrogen. The solution was cooled to -78°C. Then, LHMDS (1.46 mmol), TEMPO (190 mg, 1.22 mmol) and (diacetoxyiodo)benzene (392 mg, 1.22 mmol) were added sequentially. The solution was stirred for 6 hr at -78°C and then warmed to room temperature. After 30 min, the residue after evaporation of solvent was chromatographed with silica gel using hexane and ethyl acetate. The amount of 2c was 221 mg (57 % yield). 1H-NMR (CDCl3, 300 MHz) δ 7.38–7.19 (5H, m), 5.11 (1H, s), 4.03 (2H, q, J=7.14Hz), 1.41–1.00 (18H, m), 0.64 (3H, s), IR (KBr) 1759 (C=O) cm-1, HRMS m/z calcd for C19H30NO3 (M+H) + 320.2226, found 320.2232.
  • , When TEMPO (100 mg, 0.640 mmol) and (diacetoxyiodo)benzene (206 mg, 0.640 mmol) was heated in THF (8 mL) for 44 hrs, 2-(2,2,6,6-tetramethyl-l-piperidinyloxy)tetrahydrofuran4 (47 mg) was formed in 33 % yield.
  • Jahn, U., 1998. J. Org. Chem. 63 (1998), pp. 7130–7131.

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