Bis-heteroannulation. 16. A synthetic approach to geigerin

Furano alcohol 5, the key intermediate in our proposed synthesis of the guaianolide sesquiterpene geigerin (1), was prepared by a novel sequence of reactions which includes a chemoselective oxy-Cope transformation of enynols of general structure 42. Although 42 itself underwent oxy-Cope reaction wit...

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Bibliographic Details
Published inJournal of organic chemistry Vol. 57; no. 23; pp. 6305 - 6313
Main Authors Jacobi, Peter A., Touchette, Kim M., Selnick, Harold G.
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 01.11.1992
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
(-)-NORSECURININE
(+)-NORSECURININE
(+/-)-LIGULARONE
LACTONES
RING
ESTERS
(+/-)-GNIDIDIONE
(+/-)-PANICULIDE-A
(+/-)-PETASALBINE
FACILE SYNTHESES
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Summary:Furano alcohol 5, the key intermediate in our proposed synthesis of the guaianolide sesquiterpene geigerin (1), was prepared by a novel sequence of reactions which includes a chemoselective oxy-Cope transformation of enynols of general structure 42. Although 42 itself underwent oxy-Cope reaction with exclusive triple-bond participation, the corresponding tert-butyldimethylsilyl ether 46 gave the desired vinyl silyloxy Cope product 48 with 100% selectivity. The conversion of acetylenic oxazole 48 to 5 was then effected by a highly efficient (Diels-Alder)-(retro-Diels-Alder) transformation to generate the guaiane ketone 20, followed by hydride reduction.
Bibliography:istex:410D2D784DE9671E1AB10336E2B6299B6FEE822D
ark:/67375/TPS-LXC9JDXV-S
ISSN:0022-3263
1520-6904
DOI:10.1021/jo00049a044