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Synfacts 2019; 15(10): 1090
DOI: 10.1055/s-0039-1690649
Synthesis of Natural Products and Potential Drugs
© Georg Thieme Verlag Stuttgart · New York

Synthesis of (±)-Hirsutene

Rezensent(en):
Erick M. Carreira
,
Matthieu J. R. Richter
Curran DP. * Rakiewicz DM. University of Pittsburgh, USA
Tandem Radical Approach to Linear Condensed Cyclopentanoids. Total Synthesis of (±)-Hirsutene.

J. Am. Chem. Soc. 1985;
107: 1448-1449
CrossrefGoogle Scholar
Curran DP. * Rakiewicz DM. University of Pittsburgh, USA
Radical-Initiated Polyolefinic Cyclizations in Linear Triquinane Synthesis. Model Studies and Total Synthesis of (±)-Hirsutene.

Tetrahedron 1985;
41: 3943-3958
CrossrefGoogle Scholar
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Publikationsverlauf

Publikationsdatum:
17. September 2019 (online)

 
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Key words

(±)-hirsutene - triquinanes - Ireland–Claisen rearrangement - radical cyclization

Significance

Hirsutene is a linear triquinane that was isolated from the fungi Coriolus consors in 1976. Its lack of heteroatomic functional groups along with the presence of four contiguous stereocenters and two quaternary carbon atoms render this condensed cyclopentanoid natural product challenging. In 1985, Curran and Rakiewicz reported an elegant synthesis of (±)-hirsutene employing a late-stage radical cyclization.


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Comment

Accessed in two steps from the corresponding enone, acetate A was converted into lactone B by Ireland–Claisen rearrangement followed by phenylselenolactonization. Elimination, SN2′ reaction, and deprotection furnished carboxylic acid E. Further transformation led to iodoenyne H, which underwent 5-exo-trig/5-exo-dig radical cyclization cascade in the presence of AIBN/Bu3SnH to afford (±)-hirsutene.


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