Total synthesis of avenaol

Avenaol, isolated from the allelopathic plant black oat, was the first C 20 germination stimulant related to strigolactones. Structurally, it consisted of a bicyclo[4.1.0]heptanone skeleton containing a cyclopropane ring bearing three main chains projecting in the same direction (i.e. all -cis- subs...

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Bibliographic Details
Published in:Nature communications 2017-09, Vol.8 (1), p.674-9, Article 674
Main Authors: Yasui, Motohiro, Ota, Rina, Tsukano, Chihiro, Takemoto, Yoshiji
Format: Article
Language:English
Subjects:
639/638/403/933
639/638/403/977
639/638/77/888
Allelopathy
Allene
Chemical synthesis
Cyclopropane
Germination
Humanities and Social Sciences
Isomerization
multidisciplinary
Natural products
Organic compounds
Oxidation
Ring opening
Science
Science (multidisciplinary)
Strategy
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Summary:Avenaol, isolated from the allelopathic plant black oat, was the first C 20 germination stimulant related to strigolactones. Structurally, it consisted of a bicyclo[4.1.0]heptanone skeleton containing a cyclopropane ring bearing three main chains projecting in the same direction (i.e. all -cis- substituted cyclopropane). Herein, we report the total synthesis of avenaol using a robust strategy involving the formation of an all- cis -substituted cyclopropane via an alkylidenecyclopropane. The key factors in the success of this total synthesis include the Rh-catalysed intramolecular cyclopropanation of an allene, an Ir-catalysed stereoselective double-bond isomerisation, and the differentiation of two hydroxymethyl groups via the regioselective formation and oxidation of a tetrahydropyran based on the reactivity of a cyclopropyl group. This strategy effectively avoids the undesired ring opening of the cyclopropane ring and the formation of a caged structure. Furthermore, this study confirms the proposed structure of avenaol, including its unique all- cis -substituted cyclopropane moiety. Avenaol is a potent germination stimulant that can be extracted from black oat. Here, the authors report the total synthesis of avenaol by developing a strategy to access all- cis -substituted cyclopropanes.
ISSN:2041-1723
2041-1723
DOI:10.1038/s41467-017-00792-1