Total Syntheses of (±)- and (−)-Stemoamide

(±)-Stemoamide (1) was prepared in seven steps beginning with γ-chlorobutryl chloride (20) and succinimide (15), which were efficiently converted to the key alkyne oxazole 17 on a multigram scale. Intramolecular (Diels−Alder)−(retro-Diels−Alder) reaction of 17 then gave butenolide 12b directly upon...

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Bibliographic Details
Published inJournal of the American Chemical Society Vol. 122; no. 18; pp. 4295 - 4303
Main Authors Jacobi, Peter A, Lee, Kyungae
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 10.05.2000
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Multidisciplinary
Physical Sciences
Science & Technology
SYSTEM
BIS-HETEROANNULATION
ACID
DIELS-ALDER REACTION
ENYNE METATHESIS REACTION
(+)-CROOMINE
ADDITIONS
STEMONA ALKALOIDS
CYCLIZATION
ASYMMETRIC TOTAL SYNTHESIS
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Summary:(±)-Stemoamide (1) was prepared in seven steps beginning with γ-chlorobutryl chloride (20) and succinimide (15), which were efficiently converted to the key alkyne oxazole 17 on a multigram scale. Intramolecular (Diels−Alder)−(retro-Diels−Alder) reaction of 17 then gave butenolide 12b directly upon aqueous workup. The remaining two stereocenters in 1 were established in a single step by a highly selective reduction of 12b (NaBH4/NiCl2), followed by equilibration to the thermodynamically favored natural configuration. In analogous fashion (−)-stemoamide (1) was prepared beginning with l-pyroglutamic acid (S-35).
Bibliography:ark:/67375/TPS-LVKWQT31-C
istex:890BD030E4F689FEA990BB83967733F191D8503A
ISSN:0002-7863
1520-5126
DOI:10.1021/ja994214w