Intramolecular C-H insertion reactions of (η5-cyclopentadienyl)dicarbonyliron carbene complexes: scope of the reactions and application to the synthesis of (±)-sterpurene and (±)-pentalenene

Ishii, Shingo ; Zhao, Shikai ; Mehta, Goverdhan ; Knors, Christopher J. ; Helquist, Paul (2001) Intramolecular C-H insertion reactions of (η5-cyclopentadienyl)dicarbonyliron carbene complexes: scope of the reactions and application to the synthesis of (±)-sterpurene and (±)-pentalenene Journal of Organic Chemistry, 66 (10). pp. 3449-3458. ISSN 0022-3263

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Official URL: http://pubs.acs.org/doi/abs/10.1021/jo001792i

Related URL: http://dx.doi.org/10.1021/jo001792i

Abstract

5-Cyclopentadienyl)dicarbonyliron carbene complexes, [(η5-C5H5)(CO)2Fe=CHR]+BF4;, are generated as reactive intermediates from thioether derivatives, (η5-C5H5)(CO)2FeCH(R)SPh, by S-alkylation with trimethyloxonium tetrafluoroborate and loss of thioanisole. The carbene complexes undergo intramolecular C-H insertion into appropriately situated side chains to form cyclopentane derivatives. The reaction has been developed into a general procedure employing cycloalkanones as scaffolds bearing the iron carbene moieties and the side chains at C(2) and C(3), respectively. The products of the intramolecular insertion reactions are substituted bicyclo[n.3.0]alkanones. The scope and limitations of the reaction are described. The reaction is applied to a total synthesis of sterpurene and to a formal synthesis of pentalenene. Overall, this approach to cyclopentane annulation complements the related metal-catalyzed insertion reactions of diazocarbonyl compounds, which are also believed to occur via metal carbene complexes.

Item Type:Article
Source:Copyright of this article belongs to American Chemical Society.
ID Code:28946
Deposited On:18 Dec 2010 05:46
Last Modified:06 Mar 2011 13:04

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