Titanocene(III)-Catalyzed 6-exo Versus 7-endo Cyclizations of Epoxypolyprenes: Efficient Control and Synthesis of Versatile Terpenic Building Blocks

In this article, a complete study on the selectivity of titanocene(III) cyclization of epoxypolyprenes is presented. The requirements for the formation of six‐ or seven‐membered rings during these cyclizations are determined, taking into account the different substitution pattern in the epoxypolypre...

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Bibliographic Details
Published in:Chemistry : a European journal 2013-10, Vol.19 (43), p.14484-14495
Main Authors: Justicia, José, Jiménez, Tania, Miguel, Delia, Contreras-Montoya, Rafael, Chahboun, Rachid, Álvarez-Manzaneda, Enrique, Collado-Sanz, Daniel, Cárdenas, Diego J., Cuerva, Juan M.
Format: Article
Language:English
Subjects:
Catalysis
Chemistry
cyclic compounds
Cyclization
Derivatives
Epoxy Compounds - chemistry
Formations
Free Radicals - chemistry
natural products
Organometallic Compounds - chemistry
Oxygenated
Precursors
radicals
Selectivity
Stereoisomerism
Studies
Synthesis
Terpenes
Terpenes - chemical synthesis
Terpenes - chemistry
Thermodynamics
Titanium
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Summary:In this article, a complete study on the selectivity of titanocene(III) cyclization of epoxypolyprenes is presented. The requirements for the formation of six‐ or seven‐membered rings during these cyclizations are determined, taking into account the different substitution pattern in the epoxypolyprene precursor. Thus, a complete selectivity to 6‐exo or 7‐endo cyclization process has been achieved, yielding mono‐, bi‐, and even tricyclic compounds, constituting a new and efficient access to this type of derivative. Additionally, this procedure opens the possibility to prepare excellent building blocks for the synthesis of polycyclic compounds with a trisubstituted oxygenated function, which is present in several natural terpenes. Ti for terpenes: A complete study on the selectivity of the titanocene(III)‐catalyzed cyclization of epoxypolyprenes is presented. The requirements for the formation of six‐ or seven‐membered rings during these cyclizations are determined, yielding complete selectivity for the 6‐exo or 7‐endo cyclization process (see scheme). This procedure opens the possibility to prepare excellent building blocks for the synthesis of polycyclic compounds.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201302575