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Synthesis of the 6-Methylencarboxylic Acid Derivatives of Testosterone and Progesterone
Handschuh, Dieter,Voelter, Wolfgang
, p. 1007 - 1016 (2007/10/02)
The methyl 6β-(phenylsulfonyl)acetate and methyl 6β-(methylsulfonyl)acetate derivatives 8 and 10, respectively, of testosterone and of progesterone (9 and 11, respectively) were synthesized by allylic alkylation of the corresponding ?-allylpalladium chloride complexes 3 and 4.Chromatographic separation of the reaction mixtures yields as main products 8a and 9a with S configuration at the new asymmetric center.By-products 8b and 9b have R configuration.The corresponding by-products were not found in reaction mixtures of 10 and 11.The by-products 9c and 11c with α-configuration at C-17 (isoprogesterone derivatives) were isolated from the corresponding reaction mixtures.Alkaline treatment of the main products leads to the 6-methylenecarboxylic acid derivatives as a result of elimination and saponification: 8a and 11a gave 16 and 17.Base-catalyzed elimination of 9a yields the α,β-unsaturated methyl ester 19.NMR spectroscopic investigations (NOE, NOESY) of 19 support the predicted E configuration.
