Efficient synthesis of octandrenolone and related dipyranoacetophenones.
Octandrenolone (1) was prepared in high yield by condensation of 2', 4',6'-trihydroxyacetophenone with 3-chloro-3-methylbut-1-yne in the presence of a catalytic amount of copper(I) iodide. Methylation of 1 afforded O-methyloctandrenolone (2). Oxidation of 2 with m-chloroperoxybenzoic acid followed by hydrolysis gave the racemic trans-(+)-1-(9,10-dihydro-9,10-dihydroxy-5-methoxy-2,2,8, 8-tetramethyl-2H,8H-benzo[1,2-b:3,4-b']dipyran-6-yl)ethanone (3), which confirmed the structure of the natural product previously isolated from Melicope erromangensis.
Pernin
R
R
Laboratoire de Pharmacognosie, Faculté de Médecine et de Pharmacie, Place St. Jacques, F25030 Besançon Cedex, France.
Muyard
F
F
Bévalot
F
F
Tillequin
F
F
Vaquette
J
J
D000098:Acetophenones / Q000138:chemical synthesis* / Q000737:chemistry*; D002855:Chromatography, Thin Layer; D006868:Hydrolysis; D007202:Indicators and Reagents; D013058:Mass Spectrometry; D008745:Methylation; D010084:Oxidation-Reduction; D018517:Plant Roots / Q000737:chemistry; D010944:Plants / Q000737:chemistry; D013055:Spectrophotometry, Infrared; D013056:Spectrophotometry, Ultraviolet
D000098:Acetophenones; D007202:Indicators and Reagents; C406636:octandrenolone