Studies toward the enantioselective syntheses of oxylipins: total synthesis and structure revision of solandelactone E.
An efficient and general entry to unsaturated cyclopropane- and lactone-containing oxylipins of marine origin has been designed and applied to the first enantioselective total synthesis of solandelactone E. The synthesis, which proceeds in a total of 23 steps from commercially available materials, features a diastereoselective acetal-directed cyclopropanation of an electron-deficient diene, a regioselective Sharpless enantioselective dihydroxylation, and a stereoselective [2,3]-sigmatropic rearrangement of a selenoxide to effect a 1,3-transposition of an allylic alcohol. Comparison of spectral data for the synthetic solandelactone, thus prepared, with data in the literature led to a revision of the original structural assignments of the C(11)-epimeric solandelactones.
Davoren
Jennifer E
JE
Department of Chemistry and Biochemistry, The University of Texas, Austin, Texas 78712, USA.
Harcken
Christian
C
Martin
Stephen F
SF
D007783:Lactones / Q000138:chemical synthesis* / Q000737:chemistry*; D008968:Molecular Conformation; D054883:Oxylipins / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
D007783:Lactones; D054883:Oxylipins; C519028:solandelactone E