Biomimetic synthesis of trans,syn,trans-fused polyoxepanes: remarkable substituent effects on the endo-regioselective oxacyclization of polyepoxides.

Biomimetic synthesis of trans,syn,trans-fused polyoxepanes: remarkable substituent effects on the endo-regioselective oxacyclization of polyepoxides. Research Abstract Details 

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Biomimetic synthesis of trans,syn,trans-fused polyoxepanes: remarkable substituent effects on the endo-regioselective oxacyclization of polyepoxides. Abstract Text:

Jason C Valentine,Frank E McDonald,Wade A Neiwert,Kenneth I Hardcastle,

The biogenesis of trans,syn,trans-fused polycyclic ether substructures of neurotoxic natural products of the brevetoxin-ciguatoxin family may involve regio- and stereoselective oxacyclizations of polyepoxides. We report that a biomimetic Lewis acid-promoted cyclization of 1 to 2 proceeds with endo-regioselectivity and anti-stereospecificity at each position of nucleophilic addition (C3, C7, C11, and C15 in 1) when the tandem cyclization cascade is terminated by a carbonyl oxygen nucleophile. In contrast to expectations from earlier reports with simpler epoxide substrates, alkyl substituents are not required at internal epoxide positions corresponding to C7 and C11 in polyepoxide 1. Furthermore, we report that trimethylsilyl serves as a removable regioselectivity-directing substituent at positions corresponding to C3 of 1. These results greatly expand the potential applications of this biomimetic oxacyclization cascade to the synthesis of fused polycyclic ether natural products.

Biomimetic synthesis of trans,syn,trans-fused polyoxepanes: remarkable substituent effects on the endo-regioselective oxacyclization of polyepoxides. Publishing Authors By Initials

JC Valentine,FE McDonald,WA Neiwert,KI Hardcastle,

For similar inorganic chemicals: silicon compounds: silanes research abstracts see: inorganic chemicals: silicon compounds: silanes research

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Biomimetic synthesis of trans,syn,trans-fused polyoxepanes: remarkable substituent effects on the endo-regioselective oxacyclization of polyepoxides. Journal Published:

PUBLICATION TYPE: Research Support, U.S. Gov't,

Journal: Journal of the American Chemical Society

VOLUME: 127

Page Numbers: 4586-7

Journal Abbreviation: J. Am. Chem. Soc.

ISSN: 0002-7863

DAY: 6

MONTH: Apr

YEAR: 2005

Biomimetic synthesis of trans,syn,trans-fused polyoxepanes: remarkable substituent effects on the endo-regioselective oxacyclization of polyepoxides. Information

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LANGUAGE: eng

NlmUniqueID: 7503056

Biomimetic synthesis of trans,syn,trans-fused polyoxepanes: remarkable substituent effects on the endo-regioselective oxacyclization of polyepoxides. Keywords Mesh Terms:

KEYWORDS: Silanes

MESH TERMS: chemistry

Chemical & Substance for Abstract: Biomimetic synthesis of trans,syn,trans-fused polyoxepanes: remarkable substituent effects on the endo-regioselective oxacyclization of polyepoxides. Information

Substance Name: Silanes

Registry Number: 0

Grant and Affiliation Information for Biomimetic synthesis of trans,syn,trans-fused polyoxepanes: remarkable substituent effects on the endo-regioselective oxacyclization of polyepoxides.

AFFILIATION: Department of Chemistry, Emory University, Atlanta, GA 30322, USA.

Country: United States

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MEDLINETA: J Am Chem Soc

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