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Synthetic Communications
An International Journal for Rapid Communication of Synthetic Organic Chemistry
Volume 18, 1988 - Issue 7
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Original Articles

A Key Intermediate for the Synthesis of Antitumor Lignan Prototypes

, &
Pages 699-710 | Published online: 19 Dec 2006

References

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  • Belletire , J. L. and Spletzer , E. G. 1986 . Ibid , 27 : 131
  • Belletire , J. L. and Spletzer , E. G. 1986 . Synth. Commun. , 16 : 575
  • Rao , C. B. S. 1978 . Chemistry of Lignans , Andhra Pradish : Andhra University Press .
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  • Trumbell , E. R. and Cole , J. R. 1969 . Ibid , 58 : 176
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  • Becker , D. , Hughes , L. R. and Raphael , R. A. J. Chem. Soc., Perkin Trans. I , 1977 1674 and references cited within.
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  • M+ = 404; 1H-NMR (CDCl3: 300 MHz) (partial) δ 5.941 (minor isomer), 5.912 (major isomer) methylenedioxy CH2; IR broad OH stretch, no carbonyl peak.
  • Commercially available 3-(3,4,5-trimethoxyphenyl) propionic acid was converted into its acid chloride (IR(CCl4) vmax = 1800 cm−1) via treatment with (COCl)2 in benzene at R. T. The acid chloride was reacted with two equivalents of KH and 1 equivalent of benzenesulfonamide to give after acidification the highly crystalline acylsulfonamide 27 (mp 116–117°C) (from EtOAc); 73.6% yield; IR (CHCl3) vmax = 1730 cm−1; 1H-NMR (300 MHz, CDCl3) δ 2.45 (t, 2H), 2.8 (t, 2H), 3.75 (s, 6H), 3.85 (s, 3H), 6.3 (s, 2H), 7.5–7.7 (m, 3H), 8.05 (d, 2H), 9.25 (br s, 1H); M+ Calc'd 379.1090, Found 379.1091). Reaction of dianion 26 (derived from 27 by treatment at -78°C with 2 equiv. of n-BuLi followed by warming to 0°C over several hours) with 2-iodocarboxylate 13 (prepared from 12 by treatment with 1 equiv. NaH at 0°C) at -78°C (cannula transfer) followed by warming to R. T., evaporation of volatiles, acidification, extraction with EtOAc, and flash chromatography (SiO2) gave acid-acylsulfonamide 28 (56%) (IR v = 1730, 1705 cm−1; 1H-NMR (300 MHz, CDCl3/CD3SOCD3) 2.7–3.05 (m, 6H), 3.75 (s, 6H), 3.85 (s, 3H), 5.95 (s, 2H), 6.3 (s, 2H), 6.5–6.7 (m, 3H), 7.4–7.65 (m, 3H), 7.8–7.9 (m, 2H)). Target 9 was obtained by first treating 28 at 0°C in THF with BH3·SMe2 (1.9 equiv.) with gradual warming to R. T. over 14 hours. Removal of volatiles, addition of EtOAc/4N aq. HCl, stirring at R. T. over 4 hours, partitioning in a separatory funnel, washing with sat'd brine, drying, filtration, removal of solvent, and flash chromatography gave 9 as a pale yellow syrup (ca. 75% from 28
  • M+ Calc'd 400.1522, Found 400.1496; 1H-NMR (300 MHz, CDCl3) 2.4–2.7 (m, 4H), 2.9–3.0 (m, 2H), 3.83 (s, 9H), 3.9 (dd, 1H), 4.2 (dd, 1H), 5.93 (br s, 2H), 6.36 (s, 2H), 6.45–6.58 (m, 2H), 6.68–6.78 (m, 1H); 13C-NMR (75 MHz, CDCl3) 35.257 (t), 38.362 (t), 41.031 (d), 46.466 (d), 56.109 (q), 60.879 (q), 71.194 (t), 101.103 (t), 106.216 (d), 108.316 (d), 108.758 (d), 121.546 (d), 131.540 (s), 133.315 (s), 136.869 (s), 146.414 (s), 147.938 (s), 153.268 (s), 178.517 (s); IR vmax = 1772 (s) cm−1..
  • Hussain , S. A. M. T. , Ollis , W. D. , Smith , C. and Stoddart , J. F. J. Chem. Soc. Perkin Trans. I , 1975 1480
  • Haworth , R. D. and Atkinson , J. R. J. Chem. Soc. , 1938 797
  • Damon , R. E. , Schlessinger , R. H. and Blount , J. F. 1976 . J. Org. Chem. , 41 : 3773
  • Alternatively, isolation of the bromoacid after only a short (ca. 20 min) low temperature exposure to CBr4 followed by a careful base/acid extraction cycle performed prior to a final flash filtration leads to yellowish crystalline material of high quality.

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