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Synthesis 2019; 51(09): 1995-2000
DOI: 10.1055/s-0037-1610686
DOI: 10.1055/s-0037-1610686
paper
Selectivity Control in Terpene Rearrangements: A Biomimetic Synthesis of the Halimanic Bicyclic Core
Financial support from the Supreme Council for Science and Technology Development, Academy of Sciences of Moldova (Project No. 15.817.02.14A) is gratefully acknowledged. V.K. acknowledges the Alexander von Humboldt Foundation for a postdoctoral fellowship.Weitere Informationen
Publikationsverlauf
Received: 18. September 2018
Accepted after revision: 17. Dezember 2018
Publikationsdatum:
19. Februar 2019 (online)
Abstract
The bicyclic core of the halimanic framework is synthesized in optically active form by an acid-induced rearrangement of a homodrimanic epoxide. The substrate can follow two different pathways under acidic treatment. Using fluorosulfonic acid as a promoter at low temperature favors ring contraction to a perhydrindanic structure. In contrast, milder acids at higher temperatures bring about predominantly an angular methyl migration and formation of the halimanic bicyclic system. In particular, an acidic pillared clay selectively promoted this transformation.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1610686.
- Supporting Information
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