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Synthesis 2019; 51(09): 2001-2006
DOI: 10.1055/s-0037-1612063
DOI: 10.1055/s-0037-1612063
paper
Tungsten-Promoted Hetero-Pauson–Khand Cycloaddition: Application to the Total Synthesis of (–)-Allosecurinine
Further Information
Publication History
Received: 06 December 2018
Accepted after revision: 17 December 2018
Publication Date:
18 February 2019 (online)
Abstract
Herein, we report a concise enantioselective synthesis of (–)-allosecurinine, a tetracyclic Securinega alkaloid featuring an α,β-unsaturated γ-lactone moiety. Starting from inexpensive and readily available trans-l-hydroxyproline, our strategy entails a rare late-stage [2+2+1]-hetero-Pauson–Khand cycloaddition between a ketone and an alkyne as the key complexity-generating step to rapidly install the CD-ring system. The reported W(CO)6-promoted intramolecular cyclization provides the first example of a tungsten-mediated hetero-Pauson–Khand reaction. This approach to the strained bicyclic CD motif present in allosecurinine provides some insights into the boundaries of this potentially powerful methodology that might be further extended to other butenolide-containing natural products.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1612063.
- Supporting Information
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References
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For selected recent syntheses of securinega alkaloids, see:
For recent use of oxa-HPK in total synthesis, see: