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Synfacts 2025; 21(07): 660
DOI: 10.1055/a-2601-5680
Synthesis of Natural Products

Total Synthesis of (–)-Calidoustene

Contributor(s):
Erick M. Carreira 
,
Tristano C. Martini
Yao W, Liu Z, Ling H, Wang H, Zheng H, Wang S-H *, Zhu D-Y, Zhang S-Y, Chen X *. Lanzhou University and Peking University Shenzhen Graduate School, P. R. China
Convergent Total Synthesis of (–)-Calidoustene.

J. Am. Chem. Soc. 2025;
147: 15963-15969
DOI: 10.1021/jacs.5c03983
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Keywords

(–)-calidoustene - sesterterpenoid - Kumada cross-coupling - tandem Pummerer–Sakurai reaction - photoredox coupling - MHAT cyclization - Peterson olefination

Significance

Wang, Chen and co-workers report the first total synthesis of the sesterterpenoid (–)-calidoustene. The synthesis hinges on the construction of a bicyclo[3.2.1]octane via tandem Pummerer–Sakurai cyclization. After photoredox coupling of the bicyclo[3.2.1]octane with the trans-hydrindane moiety, the carbocyclic skeleton of the natural product is accessed by metal-hydride hydrogen atom transfer (MHAT) cyclization.


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Comment

Key allyl silane D is obtained by Kumada cross-coupling of vinyl triflate C with TMS-methylmagnesium chloride. Treatment of D with TMSOTf triggers the tandem Pummerer–Sakurai reaction, yielding bicyclo[3.2.1]octane E. After elaboration of E into aldehyde F, photoredox dual-catalysis-mediated coupling of F with vinyl bromide G afforded enone I. Subjecting I to Fe(acac)3 induces MHAT, affording ketone J. Finally, the natural product is obtained by functional group interconversions.


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Publication History

Article published online:
23 June 2025

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