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DOI: 10.1055/s-0042-1752776
Total Synthesis of (–)-Cephinoid P
Asymmetric Total Synthesis of Cephalotaxus Diterpenoids: Cephinoid P, Cephafortoid A, 14-epi-Cephafortoid A and Fortalpinoids M-N, P.
J. Am. Chem. Soc. 2023;
145: 16988-16994
DOI: 10.1021/jacs.3c05455
Key words
(–)-cephinoid P - Lindgren–Kraus oxidation - Wacker-type oxidation - Nicholas reaction - Swern oxidation - Pauson–Khand reaction - Malaprade–Lemieux–Johnson oxidation - Fétizon oxidation
Significance
The authors disclose the syntheses of several cephalotaxus C19 diterpenoids, including (–)-cephinoid P. These structurally complex natural products exhibit intriguing bioactivities, rendering them appealing targets for total synthesis. Gao and co-workers show a universal strategy via (–)-cephinoid P to access a total of six natural products.
Comment
The synthetic endeavor commenced with the preparation of propargylic alcohol E. The Lewis acidic activation of the dicobalt hexacarbonyl complex triggered nucleophilic attack of the allyl-silane, reminiscent of a Hosomi–Sakurai reaction, forming intermediate F. Introduction of the bridgehead ketone and i-Pr-ketal paved the way to the Pauson–Khand reaction, yielding (–)-cephinoid P after four additional steps. From there, five additional natural products were accessed.
Publikationsverlauf
Artikel online veröffentlicht:
14. September 2023
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