Comparative Diels-Alder reactivities within a family of valence bond isomers: a biomimetic total synthesis of (+/-)-UCS1025A.

Comparative Diels-Alder reactivities within a family of valence bond isomers: a biomimetic total synthesis of (+/-)-UCS1025A. Research Abstract Details 

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Comparative Diels-Alder reactivities within a family of valence bond isomers: a biomimetic total synthesis of (+/-)-UCS1025A. Abstract Text:

Thomas R Hoye,Vadims Dvornikovs,

A synthesis of the structurally fascinating fungal metabolite UCS1025A (1) was accomplished. It features a likely biomimetic approach to the octalin subunit via an intramolecular Diels-Alder (IMDA) reaction of a putative triene precursor (2), preceded by an efficient construction of the bisheteratriquinane subunit within that compound. Specifically, an intramolecular silyl triflate-induced cyclization of an in situ-generated silyl ketene acetal onto an imide carbonyl group (e.g., 7 to 8) was developed. The IMDA relative reactivities of a family of valence bond isomers, each differing in the precise nature of the dienophilic subunit, were determined. Under biologically relevant conditions (D2O, pH 7.2 buffer, ca. 25 degrees C), triene 2, via its lactone ring-opened congener, underwent very fast (t1/2 = 10 min) conversion to the ring-opened forms of 1 (i.e., 5a) and the tetraepimeric, alternative endo-adduct, 3 [i.e., (tetraepi)-5a].

Comparative Diels-Alder reactivities within a family of valence bond isomers: a biomimetic total synthesis of (+/-)-UCS1025A. Publishing Authors By Initials

TR Hoye,V Dvornikovs,

For similar heterocyclic compounds: alkaloids: pyrrolizidine alkaloids research abstracts see: heterocyclic compounds: alkaloids: pyrrolizidine alkaloids research

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Comparative Diels-Alder reactivities within a family of valence bond isomers: a biomimetic total synthesis of (+/-)-UCS1025A. Journal Published:

PUBLICATION TYPE: Research Support, N.I.H., Extr

Journal: Journal of the American Chemical Society

VOLUME: 128

Page Numbers: 2550-1

Journal Abbreviation: J. Am. Chem. Soc.

ISSN: 0002-7863

DAY: 1

MONTH: Mar

YEAR: 2006

Comparative Diels-Alder reactivities within a family of valence bond isomers: a biomimetic total synthesis of (+/-)-UCS1025A. Information

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LANGUAGE: eng

NlmUniqueID: 7503056

Comparative Diels-Alder reactivities within a family of valence bond isomers: a biomimetic total synthesis of (+/-)-UCS1025A. Keywords Mesh Terms:

KEYWORDS: Pyrrolizidine Alkaloids

MESH TERMS: chemical synthesis

Chemical & Substance for Abstract: Comparative Diels-Alder reactivities within a family of valence bond isomers: a biomimetic total synthesis of (+/-)-UCS1025A. Information

Substance Name: UCS 1025A

Registry Number: 0

Grant and Affiliation Information for Comparative Diels-Alder reactivities within a family of valence bond isomers: a biomimetic total synthesis of (+/-)-UCS1025A.

AFFILIATION: Department of Chemistry, University of Minnesota, Minneapolis, 55455, USA. hoye@chem.umn.edu

Country: United States

AGENCY: United States NIGMS

GRANT: GM-65597

ACRONYM: GM

MEDLINETA: J Am Chem Soc

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