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Synfacts 2022; 18(07): 0703
DOI: 10.1055/s-0041-1738542
DOI: 10.1055/s-0041-1738542
Synthesis of Natural Products and Potential Drugs
Total Synthesis of (–)-Phaeocaulisin A
Péter Á,
Crisenza GE. M,
Procter DJ.
*
The University of Manchester, UK
Asymmetric Total Synthesis of (−)-Phaeocaulisin A.
J. Am. Chem. Soc. 2022;
144: 7457-7464
DOI: 10.1021/jacs.2c02188.
Asymmetric Total Synthesis of (−)-Phaeocaulisin A.
J. Am. Chem. Soc. 2022;
144: 7457-7464
DOI: 10.1021/jacs.2c02188.
Key words
(–)-phaeocaulisin A - guaiane type sesquiterpenes - carbometalation - Sharpless asymmetric dihydroxylation - Grignard addition - samarium(II) iodide - SmI2-mediated cyclization
Significance
Procter and co-workers report the first total synthesis of the guaiane type sesquiterpene (–)-phaeocaulisin A in 19 steps. The natural product exhibits anti-inflammatory and anticancer activity which is likely linked to the bridged acetal moiety.
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Comment
On the one hand, chemoselective reduction of the ketone in N requires a tert-butyl ester to render the latter unreceptive for SET. On the other hand, SmI2-mediated cyclization of R requires the methyl ester, otherwise the lactone in S does not form. Desaturation of S is achieved by α‑bromination of the γ-lactone and elimination with silver acetate.
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Publication History
Article published online:
15 June 2022
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