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Total Synthesis of (±)-Caryopincaolide A
Chui-Chang Kong1,2, Wan-Ning Yuan1,2, Yuan Sun1,2
1School of Chemistry and Environment, Yunnan Minzu University, Kunming650500, P. R. China.
None:
The first total synthesis of (±)-caryopincaolide A, a rearranged abeo-abietane diterpenoid containing a 5/6/6 fused skeleton and three contiguous all-carbon quaternary centers, is described. The route installs the aromatic ring at an early stage and assembles the congested framework in a C/B → A sequence. An Fe(acac)3/PhSiH3-mediated reductive alkene-enone coupling is the key skeleton-forming step, providing the rearranged tricyclic core in 93% yield. Carbonyl transposition, β-keto ester alkylation, ketone hydrogenolysis, and an ortho-quinone-mediated aromatization/lactonization sequence complete the synthesis in 16 steps and 3.0% overall yield.
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