Asymmetric Total Synthesis of (−)-Vinigrol

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  • Published: 03 October 2019
  • Copyright: Wiley-VCH Verlag GmbH & Co. KGaA
  • Source / Publisher: Journal of the American Chemical Society/ACS Publications
  • Associated Societies: American Chemical Society (ACS), USA
thumbnail image: Asymmetric Total Synthesis of (−)-Vinigrol

(−)-Vinigrol (pictured) is a structurally complex diterpene and was isolated from a fungus. The compound has an unprecedented rigid 1,5-butanodecahydronaphthalene core with eight contiguous stereocenters. In addition, it contains a bicyclo[5.3.1]-undecane ring system, which is also found in the well-known terpene taxol. Vinigrol has potentially useful biological activities, but is challenging to synthesize.

Chuang-Chuang Li, Southern University of Science and Technology, Shenzhen, China, and colleagues have performed an asymmetric total synthesis of (−)-vinigrol. The team started from commercially available chloro-dihydrocarvone. This starting material was converted to a furane and functionalized using a Grignard reaction and a hydroxymethylation. An oxidative rearrangement, followed by an intramolecular [5+2] cycloaddition, then gives a bicyclo[5.4.1]dodecane skeleton. A ring contraction was the key step in converting this intermediate to the desired (−)-vinigrol.

The synthesis involves a linear sequence of 14 steps from chloro-dihydrocarvone and avoids the need for protecting groups. According to the researchers, it includes the first example of an intramolecular [5+2] cycloaddition to construct eight-membered ring systems in natural product synthesis. The approach should also allow the preparation of further vinigrol analogues.


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