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DOI: 10.1039/A808072K (Paper) Reference Section for: Chem. Commun., 1999, 187-188

Unexpected formation of 3,3a,4,7a-tetrahydrobenzofuran-2,5-diones as well as arene carboxylic acids upon formal double exo nucleophilic addition of R1R2C–COO– to anisolechromium tricarbonyl complexes

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Moncef Bellassoued, Evelyne Chelain, Jérôme Collot, Henri Rudler and Jacqueline Vaissermann

Abstract

Bis(trimethylsily)ketene acetals of the general structure 2 (R1 = H, Me, R2 = Me, Et, Pri, CMe=CH2) react at –78 °C in the presence of ButOK with a series of arenechromium tricarbonyl complexes 3 to give as expected, after oxidation with I2 followed by silica gel chromatography, arylcarboxylic acids 7. In the case of anisolechromium tricarbonyl 8, besides the m-methoxyarylcarboxylic acids, tetrahydrobenzofuran-2,5-diones 11, are formed as the result of a double nucleophilic addition.

References

  1. M. F. Semmelhack, Comprehensive Organic Synthesis, ed. B. M. Trost and I. Fleming, Pergamon, Oxford, 1991, vol. 4, p. 517 Search PubMed; E. P. Kündig, Pure Appl. Chem., 1985, 57, 1855 Search PubMed.
  2. M. F. Semmelhack and H. T. Hall, J. Am. Chem. Soc., 1974, 96, 7091 CrossRef CAS.
  3. R. J. Card and W. S. Trayhanovsky, Tetrahedron Lett., 1973, 3823 CrossRef CAS.
  4. A. Parlier, M. Rudler, H. Rudler, R. Goumont, J. C. Daran and J. Vaissermann, Organometallics, 1994, 13, 4708 CrossRef CAS.
  5. C. Ainsworth and Y. N. Kuo, J. Organomet. Chem., 1973, 46, 73 CrossRef CAS.
  6. M. Bellassoued and M. Gaudemar, Tetrahedron Lett., 1990, 31, 209 CrossRef CAS.
  7. Selected data for 4: δH(200 MHz, CDCl3) 7.32–7.27 (m, 3H), 7.05–7.01 (m, 5H), 6.85–6.95 (m, 1H), 4.13 (q, J 8, 2H), 1.55 (s, 6H), 1.17 (t, J 8, 3H). δC(50 MHz, CDCl3) 176.42, 157.12, 147.08, 129.7, 129.55, 123.21, 120.64, 118.7, 111.7, 60.90, 46.50, 26.51, 14.08. MS (EI)m/z 284 (M+). For 6: δH(200 MHz, CDCl) 7.40–7.25 (m, 5H), 4.50–4.25 (m, 2H), 3.60 (dd, J 9.5, 1H), 2.77–2.61 (m, 1H), 2.51–2.35 (m, 1H). δC(50 MHz, CDCl3) 177.6, 136.76, 128.62, 128.0, 127.7, 66.64, 45.57, 31.64. MS (EI)m/z 212 (M+). For 7(R = OPh): δH(200 MHz, CDCl3) 11.0 (br s, 1H), 7.38–6.87 (m, 9H), 3.49 (t, J 6, 1H), 2.10 (m, 1H), 1.77 (m, 1H), 0.92 (t, J 7.2, 3H). δC(50 MHz, CDCl3) 180.43, 157.50, 157.07, 149.43, 129.87, 123.44, 123.87.44, 123.0, 119.01, 118.82, 117.70, 53.30, 26.40, 12.20. MS (EI)m/z 256 (M+). For 11a: mp 69 °C; δH(200 MHz, CDCl3) 6.84 (dd, J 10.2, 3.4, 1H), 6.14 (d, J 10.2, 1H), 5.10 (dd, J 3.4, 0.8, 1H), 2.81 (dd, J 13.8 and 6.4, 1H), 2.51 (ddd, J 13.8, 10.6 and 6.4), 1.25 (s, 3H), 1.09 (s, 3H). δC(50 MHz, CDCl3) 196.17, 180.24, 141.61, 132.12, 70.97, 43.32, 35.25, 24.71, 20.05.
  8. Crystal data for 11a: colorless plates monoclinic space group P21/n, a= 11.369(3), b= 6.145(3), c= 13.537(4)Å, β= 105.53(2)°, Z= 4, R= 0.0476, Rw*= 0.0564, GOF = 1.11. Collected reflections 2505, independent reflections, 2186 (θ= 1–28 °, Mo-Kα radiation, Rint= 0.0079). The obtained structure model was first refined anisotropically for all non-hydrogen atoms and isotropically for the hydrogen atoms using 1549 reflections. CCDC 182/1116.
  9. M. F. Semmelhack, J. J. Harrison and Y. Thebtaranonth, J. Org. Chem., 1979, 44, 3275 CrossRef CAS.
  10. J. C. Boutonnet, F. Rose-Munch and E. Rose, Tetrahedron Lett., 1985, 26, 3989 CrossRef CAS.
  11. M. F. Semmelhack and A. Yamashita, J. Am. Chem. Soc., 1980, 102, 5924 CrossRef CAS.
  12. H. G. Schmalz and K. Schellhaas, Angew. Chem., Int. Ed. Engl., 1997, 35, 2146 CrossRef CAS.
  13. A. J. Pearson and A. V. Gontcharov, J. Org. Chem., 1998, 63, 152 CrossRef CAS.
  14. M. F. Semmelhack, H. T. Hall, M. Yoshifuji, G. Clark, T. Bargar and K. Hirotsu, J. Am. Chem. Soc., 1979, 101, 3535 CrossRef CAS.
  15. E. P. Kündig and D. P. Simmons, J. Chem. Soc., Chem. Commun., 1983, 1320 RSC.
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