The structure and function of oestrogens. V. Synthesis of (9,12,12-2H3)- and (11ζ 12,12-2H3)-oestradiol

1983 ◽  
Vol 36 (2) ◽  
pp. 403 ◽  
Author(s):  
DJ Collins

17,17-Ethylenedioxy-3-methoxy(9,12,12-2H3)-9β-oestra-l,3,5(10)-trien-11-one (3) was reduced to the mixture of 11-epimeric alcohols (4) which upon elimination of DHO gave the (12,12-2H2)-9(11)- dehydrooestrone derivative (5b). Treatment of (5b) with (2H6)diborane followed by oxidation afforded the (9,12,12-2H3)alcohol (8a); hydride reduction of the corresponding tosylate then gave 17,17-ethylenedioxy-3-methoxy(9,12,12-2H3)oestra-l,3,5(l0)-triene (7). Acid hydrolysis of (7), followed by demethylation, and reduction with sodium borohydride yielded (9,12,12-2H3)oestradiol (10). Sodium borohydride reduction of (11&12,12-2H3)oestrone (6),prepared in several steps from the 9β,12,12-trideutero ketone (3), gave (11 ξ,12,12-2H3)oestradiol (9). [The two trideuterated oestradiols (9) and (10) were required for biological studies.]

1970 ◽  
Vol 48 (14) ◽  
pp. 2234-2245 ◽  
Author(s):  
Edward Piers ◽  
Kin Fai Cheng

Lithium–ammonia reduction of the hydroguaiazulene derivative 6, followed by oxidation of the resulting diol 13, gave, in a highly stereoselective manner, the keto alcohol 14. The latter was converted into 5-epi-α-bulnesene (2). In a similar sequence of reactions, 4-epi-α-bulnesene (3) was obtained from compound 9. Photochemical rearrangement of the previously obtained dienone 25 gave the hydroguaiazulene derivative 27. Successive subjection of the latter to acetylation, hydrogenation, and sodium borohydride reduction gave a mixture of the epimeric diols 31 and 32. When this mixture was treated with p-toluenesulfonic acid in pyridine, and the resulting olefinic diester 35 was sequentially subjected to hydrogenation [tris(triphenylphosphine)chlororhodium] and lithium aluminum hydride reduction, the crystalline diol 37 was obtained. The latter was converted into α-bulnesene (1) by standard reactions.


Sign in / Sign up

Export Citation Format

Share Document