Diterpenoid total synthesis—XIX : (±)-Steviol and erythroxydiol A: Rearrangements in bicyclooctane compounds

Abstract (±)-Steviol (I) and erythroxydiol A (II), tetracyclic diterpenes with a substituent at the bridgehead C-13 position, were synthesized by using two interesting rearrangement reactions (XII → XIV and XVI → XVII, respectively).

[1]  K. Schreiber,et al.  Gibberelline—XII: Zur umlagerung von 8,15-epoxy-gibberellinsäure☆ , 1968 .

[2]  H. G. Fletcher,et al.  STEVIOSIDE. I. THE STRUCTURE OF THE GLUCOSE MOIETIES , 1955 .

[3]  L. Mander,et al.  Experiments directed toward the total synthesis of terpenes. IX. The total synthesis of (+or-)-hibaene and the oxygenation of some tetracyclic diterpenes. , 1966, The Journal of organic chemistry.

[4]  K. Mori.  Synthesis of substances related to Gibberellins—XXIV : Total synthesis of (±)-epiallogibberic acid☆ , 1971 .

[5]  K. Schreiber,et al.  Gibberelline—IX : Epoxydation von einigen gibberellinen , 1966 .

[6]  P. Bartlett,et al.  Some Reactions of Δ2-Cyclohexenone, Including the Synthesis of Bicyclo(2,2,2)-octanedione-2,6 , 1940 .

[7]  R. Coates,et al.  Structural modifications of isosteviol. Partial synthesis of atiserene and isoatiserene , 1971 .

[8]  J. R. Hanson,et al.  The chemistry of the tetracyclic diterpenoids—V : Stereochemical studies in the stachene series , 1967 .

[9]  J. R. Hanson,et al.  The chemistry of the tetracyclic diterpenoids—VI : The stereochemistry of some reactions of (−)-kaurene , 1967 .

[10]  E. Corey,et al.  Total synthesis of prostaglandins F2-alpha and E2 as the naturally occurring forms. , 1970, Journal of the American Chemical Society.

[11]  E. Mosettig,et al.  OPTICAL ROTATORY DISPERSION STUDIES. LVIII.1 THE COMPLETE ABSOLUTE CONFIGURATIONS OF STEVIOL, KAURENE AND THE DITERPENE ALKALOIDS OF THE GARRYFOLINE AND ATISINE GROUPS2 , 1961 .

[12]  R. Bell,et al.  Experiments Directed toward the Total Synthesis of Terpenes. VIII. The Total Synthesis of (±)-Kaurene and (±)-Atisirene1 , 1966 .

[13]  E. Mosettig,et al.  STEVIOSIDE. II. THE STRUCTURE OF THE AGLUCON , 1955 .

[14]  E. Mosettig,et al.  The Absolute Configuration of Steviol and Isosteviol , 1963 .

[15]  E. Corey,et al.  New methods for carbocyclic synthesis applicable to the gibberellic acids. Steroselective introduction of the angular vinyl grouping and pinacolic cyclization of keto aldehydes , 1971 .

[16]  G. Stork,et al.  A New Cyclization. 2-Methylenecyclopentanols by the Chemical Reduction of γ-Ethinyl Ketones , 1965 .