Formal Total Synthesis of Salvinorin A
ChemistryOpen October 26, 2022 DOI: 10.1002/open.202200015 (opens in new tab)
Study at a glance
AI-extracted from the abstract| Characteristics | Peer reviewed |
|---|---|
| Topics | Salvia divinorum |
| Keywords | Cyanohydrin Decalins Johnson-claisen rearrangement Wieland-miescher ketone |
| Key points | The Johnson-Claisen rearrangement of an allyl alcohol derived from a Wieland-Miescher ketone produced two diastereomeric 1,4-unsaturated esters in a ratio of approximately 2.6:1, and the major isomer was converted to a key intermediate of the Hagiwara synthesis of salvinorin A. |
Abstract
Abstract The generation of the quaternary stereocenter at the C9 position of salvinorin A precursors by the Claisen rearrangement was investigated. The required allyl alcohol was prepared from a Wieland‐Miescher ketone using a known γ‐hydroxylation, reduction of the enone double bond, cyanohydrin formation, and elimination, yielding an unsaturated nitrile. A two‐step reduction led to the required allyl alcohol. The subsequent Johnson‐Claisen rearrangement provided a mixture of two diastereomeric 1,4‐unsaturated esters in a ratio of around 2.6 : 1. The major isomer could be converted to a key intermediate of the Hagiwara synthesis of salvinorin A.