Connecting C-19 Norditerpenoids to C-20 Diterpenes: Total Syntheses of 6-Hydroxy-5,6-dehydrosugiol, 6-Hydroxysugiol, and Taiwaniaquinone H, and Formal Synthesis of Dichroanone
Oxidation of the B-ring of abietane derivatives by Sharpless dihydroxylation gave the natural products 6-hydroxy-5,6-dehydrosugiol and 6-hydroxysugiol. Moreover, further oxidation gave a hydroxy dione derivative that provides a synthetic entry into the C-19 taiwaniaquinoid family of natural products. This route is based on biosynthetic considerations and involves a benzilic acid rearrangement followed by decarboxylation. On the basis of this approach, a total synthesis of (-)-taiwaniaquinone H and a formal synthesis of (-)-dichroanone have been achieved.
Keywords: terpenoids ; biomimetic synthesis ; biosynthesis ; oxidations ; stereoselective synthesis ; total synthesis ; Catalyzed Asymmetric Dihydroxylation ; Gibberella-Fujikuroi ; Efficient Route ; Tertiary Amide ; Methyl-Ether ; Acid ; (+/-)-Dichroanone ; (+/-)-Taiwaniaquinol-B ; Cryptomerioides ; Biosynthesis
Record created on 2011-12-16, modified on 2016-08-09