Journal ArticleDOI
Tricyclo[3.3.0.02,8]octan‐3‐ones: Photochemically Prepared Building Blocks for Enantiospecific Total Syntheses of Cyclopentanoid Natural Products
Martin Demuth,Kurt Schaffner +1 more
TLDR
The tricyclo[3.3.0.2] octan-3-one as mentioned in this paper is a simple building block that can be used to obtain a wide range of cyclopentanoid structures.Abstract:
Bi- and tricyclopentanoid natural products have been in the focus of synthetic interest in recent years. With widely applicable building blocks lacking, most work has been restricted in the past to specific approaches to single racemic target structures. A novel concept is now presented which uses for the first time a simple building block, tricyclo[3.3.0.02,8]octan-3-one, providing enantiospecific access to diverse cyclopentanoid structures. Tricyclooctanone is obtained in a few steps and in high yield from benzene, via the triplet-sensitized oxadi-π-methane rearrangement of bicyclo[2.2.2]octenone as a photochemical key reaction. Smooth preparations of both enantiomers are possible by resolving the racemic mixture and of the bicyclooctenone. Owing to its structural properties the tricyclooctanone undergoes a wide array of regio- and stereoselective transformations in high yields, in compliance with the expectations for a synthetic key compound of general applicability. The total syntheses of boschnialactone, allodolicholactone, irido- and isoiridomyrmecin, and loganin aglucone 6-acetate provide the first examples of successful applications. Promising entries to coriolin, 6a-carbaprostacyclin and homologs, and 6,11-dehydroestrone complement this review of the potential of tricyclooctanone as a versatile building block for the enantiospecific total synthesis of polycyclopentanoids and related compounds.read more
Citations
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Journal ArticleDOI
Cobalt‐Mediated [2 + 2 + 2]‐Cycloadditions: A Maturing Synthetic Strategy [New Synthetic Methods (43)]
TL;DR: Dicarbonyl (η5-cyclopentadienyl)cobalt functions as a matrix on which a variety of unsaturated organic substrates undergo mutual bond formation as mentioned in this paper.
Journal ArticleDOI
Photochemical reactions as key steps in natural product synthesis
Thorsten Bach,Jörg P. Hehn +1 more
TL;DR: The most important photochemical transformations that have been employed in natural product synthesis are presented and selected total syntheses are discussed as examples, with particular attention given to the photochemical key step and its stereoselectivity.
Journal ArticleDOI
Cobalt-vermittelte [2+2+2]-Cycloadditionen: eine ausgereifte Synthesestrategie
TL;DR: In vielen Fallen verlaufen diese Reaktionen with bemerkenswerter Chemo-, Regio-and Stereoselektivitat, die zum Teil durch Trimethyl-silylsubstituenten als kontrollierende und dirigierenden Gruppen ermoglicht werden as mentioned in this paper.
Journal ArticleDOI
Synthetic Aspects of the Di-pi-methane Rearrangement.
Journal ArticleDOI
Photochemische Reaktionen als Schlüsselschritte in der Naturstoffsynthese
Thorsten Bach,Jörg P. Hehn +1 more
TL;DR: In this article, die wichtigsten Umsetzungen der photochemie vorgestellt, die auf breiter Front Einzug in die Naturstoffsynthese gehalten haben.
References
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The chemical structure of prostaglandin X (prostacyclin)
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