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Synthetic Communications
An International Journal for Rapid Communication of Synthetic Organic Chemistry
Volume 28, 1998 - Issue 4
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Original Articles

Facile Syntheses of (2R,3R)-(−)- and (2S,3S)-(+)-Chicoric Acids

He Zhao Laboratory of Medicinal Chemistry, Division of Basic Sciences, National Cancer Institute, Building 37, Room 5C06, National Institutes of Health, Bethesda, MD, 20892
&
Terrence R. Burke Jr. Laboratory of Medicinal Chemistry, Division of Basic Sciences, National Cancer Institute, Building 37, Room 5C06, National Institutes of Health, Bethesda, MD, 20892
Pages 737-740 | Received 13 Aug 1997, Published online: 02 Sep 2006

References

  • Scarpati , M. L. and Oriente , G. 1958 . Tetrahedron , 4 : 43 – 48 .
  • Robinson , W. E. Jr. , Cordeiro , M. , Abdel-Malek , S. , Jia , Q. , Chow , S. A. , Reinecke , M. G. and Mitchell , W. M. 1996 . Mol. Pharm. , 50 : 846 – 855 .
  • Robinson , W. E. Jr. , Reinecke , M. G. , Abdel-Malek , S. , Jia , Q. and Chow , S. A. 1996 . Proc. Natl. Acad. Sci. U.S.A. , 93 : 6326 – 6331 . (No experimental details were provided for the synthesis of L-chicoric acid.)
  • Zhao , H. , Neamati , N. , Mazumder , A. , Sunder , S. , Pommier , Y. and Terrence Burke , R. Jr. 1997 . J. Med. Chem. , 40 : 1186 – 1194 .
  • Compound 5 has been previously prepared (for example: Haslam E. Makinson G. K. Naumann M. O. Cunningham J. J. Chem. Soc. 1964 2137.) It is easily synthesized on large scale by treatment of 3,4-dihydroxycinnamic acid with acetic anhydride (10 equivalents) in pyridine (v/v = 5:1) in the dark overnight at room temperature. Upon removal of solvent, residue is crystallized from EtOAc:hexane to provide diacetyl caffeic acid as a white solid. Reflux (3 h) with thionyl chloride (5 equivalents) in benzene (v/v = 8:1) provides 5 upon removal of solvent.
  • Mp 153–155 °C; [α]25 D −14° (CHCl3, c 0.51); 1H NMR (250 MHz, CDCl3) δ 7.73 (d, J = 16.0 Hz, 2H), 7.44–7.36 (m, 4H), 7.24 (d, J = 8.3 Hz, 2H), 6.50 (d, J = 16.0 Hz, 2H), 5.79 (s, 2H), 2.30 (s, 6H), 2.28 (s, 6H), 1.41 (s, 18 H); FABMS m/z 756 (MH)+. Anal. calcd. for C38H42O16: C, 60.47; H, 5.61. Found: C, 60.38; H, 5.65.
  • Mp 186–188 °C; [α]25 D −159° (MeOH, c 0.16); 1H NMR (250 MHz, DMSO-d6) δ 7.81 (d, J = 1.8 Hz, 2H), 7.76–7.70 (m, 4H), 7.34 (d, J = 8.4 Hz, 2H), 6.78 (d, J = 16.2 Hz, 2H), 5.74 (s, 2H), 2.28 (s, 12H); FABMS m/z 644 (MH)+. Anal. calcd. for C30H26O16: C, 56.08; H, 4.08. Found: C, 55.82; H, 4.17.
  • 8. Mp 204–206 °C; [α]25 D −333° (MeOH, c 0.10; lit.1 −384.2° (MeOH, c 1.075)); 1H NMR (250 MHz, DMSO-d6) δ 9.69 (s, 2H), 9.16 (s, 2H), 7.55 (d, J = 15.8 Hz, 2H), 7.09–7.07 (m, 4H), 6.77 (d, J = 8.6 Hz, 2H), 6.36 (d, J = 15.9 Hz, 2H), 5.67 (s, 2H); FABMS m/z 475 (MH)+. Anal. calcd. for C22H18O12·7/4H2O: C, 52.23; H, 4.28. Found: C, 52.07; H, 4.33.
  • [α]25 D +340° (MeOH, c 0.14). Other physical data were identical to that displayed by 2.

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