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Total Synthesis of Clovan-2,9-dione via [3 + 2 + 1] Cycloaddition and Hydroformylation/Aldol Reaction
Yi Zhou1, Jun-Long Qin1, Wenbo Xu1
1Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China.
Abstract:
Here we report the total synthesis of clovan-2,9-dione via Rh-catalyzed [3 + 2 + 1] cycloaddition/hydroformylation/aldol reaction. The [3 + 2 + 1] reaction of 1-yne-vinylcyclopropane and CO was used for the generation of a 5/6 bicyclic skeleton with a bridgehead vinyl group. The hydroformylation reaction converted the congested olefin of the [3 + 2 + 1] cycloadduct to a one-carbon elongated aldehyde, which underwent in situ aldol reaction, with the carbonyl group in the [3 + 2 + 1] cycloadduct, to generate the tricyclic bridged-ring skeleton of the target molecule.
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