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Published on: January 15, 2018
Total Synthesis of (±)-Crokonoid A
Tristano Martini1, Nobel Saab1, Jonathan Muschietti1
1Department of Chemistry and Applied Biosciences, Laboratory of Organic Chemistry, 8093 Zürich, Switzerland.
Abstract:
We report the first total synthesis of (±)-crokonoid A, a highly oxidized and rearranged ent-kauranoid featuring a novel tricyclo[4.4.1.11,4]dodecane scaffold. The unique double bridged carbon skeleton was assembled by synthesis of the bicyclo[4.3.1]decane via nitrile-oxide dipolar cycloaddition. Salient features of this strategy are the effective construction of the bridged system and masking the twofold aldol motif as an isoxazoline. An unconventional bridgehead propargylation set the key quaternary stereocenter concomitant with the installation of the side chain. Subsequent cycloalkenylation led to construction of the bicyclo[3.2.1]octane, completing the carboskeleton. Strategic orchestration involving regio- and diastereoselective reactions furnished the unique oxidation pattern, thus completing the total synthesis.
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