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Synthetic Communications
An International Journal for Rapid Communication of Synthetic Organic Chemistry
Volume 6, 1976 - Issue 1
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Original Articles

An Alternative Prostaglandin Analog Synthesis Strategy:1 An Initial α-Ylation Sequence for Bis-Unsaturated Prostaglandins

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Pages 33-38 | Received 23 Sep 1975, Published online: 05 Dec 2006

References

  • The synthesis of specific prostaglandin analogs is supported by NICH & HD contract #N01‐ND‐4‐‐2839. The support of NIH grant GM‐20848 is also acknowledged
  • Alfred , P. and Sloan Foundation Fellow . 1972–1974 . Camille and Henry Dreyfus Teacher‐Scholar, 1974–1979
  • Magerlein , B. J. , DuCharme , D. W. , Magee , W. E. , Miller , W. L. , Robert , A. and Weeks , J. R. 1973 . Prostaglandins , 4 : 143
  • Labhsetwar , A. P. 1972 . Prostaglandins , 2 : 375
  • Binder , D. , Bowler , J. , Brown , E. D. , Crossley , N. S. , Hutton , J. , Senior , M. , Slater , L. , Wilkinson , P. and Wright , N. C. A. 1974 . Prostaglandins , 6 : 87
  • Corey , E. J. , Albonico , S. M. , Koelliker , U. , Schaaf , T. K. and Varma , R. K. 1971 . J. Amer. Chem. Soc. , 93 : 1491 and ref. therein
  • Schaaf , T. K. and Corey , E. J. 1972 . J. Org. Chem. , 37 : 2921 C. Doria, P. Gaio, and C. Gandolfi, Tet. Let., 4307 (1972)
  • Gandolfi , C. , Doria , G. and Gaio , P. 1972 . Tetrahedron Letters , : 2063 Reported values for the natural‐series enantiomer: mp 129.5–131°, αD ‐87.5°, mp 130–131°, αD ‐87.3° [ref. 6]
  • Corey , E. J. and Venkateswarlu , A. 1974 . J. Amer. Chem. Soc. , 94 : 6190
  • Rotatory data, and nmr spectroscopy support the structure shown. The molecular formula are confirmed either by combustion analysis or by mass spectroscopy ( 0.003 amu)
  • The removal of biphenylcarbonyl groups by this and related procedures after α‐ylation is not as efficient
  • All compounds from IIb — V, and beyond, are mixtures of diastereomers at the anomeric carbon of the THP group (s), and are typically viscous oils, or if crystalline mixtures, were not recrystallized since we did not wish to enrich the diastereomeric mixture at the expense of over‐all yield
  • The anomeric diastereomers show notably different chemical shifts for this proton resonance; see note 12
  • Ratcliffe , R. and Rodehorst , R. 1970 . J. Org. Chem. , 35 : 4000 see also J. C. Collins, W. W. Hess, and F. J. Frank, Tetrahedron Letters, 3363 (1968)
  • Andersen , N. H. , Ramwell , P. W. , Leovey , E. M. K. and Johnson , M. in press . Adv. Prostaglandin Thromboxane Res. 1 ,
  • Andersen , N. H. 1969 . J. Lipid Res. , 10 : 316
  • Andersen , N. H. and Leovey , E. M. K. 1974 . Prostaglandins , 6 : 361
  • Full details for 11,15‐epi‐PGF2a have not been reported. The 11,15‐bis‐THP derivative was used by Corey, Weinshenker et al.18 in a synthesis of ent‐11,15‐epi‐PGE2. Hydrolysis of this derivative gives material showing αD = ‐72° (THF) Δσ196 = ‐2.7 (EtOH) — which served as an authentic sample for HPLC16b and CD19 studies. The Me ester has been reported:20 αD ‐73°. For 11‐epi‐F2 compounds large rotations are the usual, with the free acids showing enhanced rotation — ent‐11‐epi‐PGF2α ester, αD ‐76°20; nat‐11‐epi‐PGF2α acid, αD +81°21a, +89°21b
  • Corey , E. J. , Terashima , S. , Ramwell , P. W. , Jessup , R. , Weinshenker , N. M. , Floyd , D. M. and Crosby , G. A. 1972 . J. Org. Chem. , 37 : 3043
  • Leovey , E. M. K. 1975 . Ph.D. Thesis Washington . reported in part as E. M. K. Leovey and N. H. Andersen, J. Amer. Chem. Soc. 97, 4148 (1975)
  • Cooper , E. L. and Yankee , E. W. 1974 . J. Amer. Chem. Soc. , 96 : 5876
  • Floyd , D. M. , Crosby , G. A. and Weinshenker , N. M. 1972 . Tetrahedron Letters , 3265 : 3269
  • Corey , E. J. , Nicolaou , K. C. and Shibasaki , M. 1975 . J. C. S. Chem. Commun. , : 658

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