Cyclomagnesation of dienes catalyzed by a chiral ansa-zirconocene

Martín, Sandra; Brintzinger, Hans-Herbert

Cyclomagnesation of dienes catalyzed by a chiral ansa-zirconocene

Dateien

Martin_238852.pdfGröße: 292.69 KBDownloads: 247

Datum

1998

Autor:innen

Martín, Sandra

Brintzinger, Hans-Herbert

Open Access-Veröffentlichung

Open Access Green

Sammlungen

Chemie

Publikationstyp

Zeitschriftenartikel

Publikationsstatus

Published

Erschienen in

Inorganica Chimica Acta. 1998, 280(1-2), pp. 189-192. ISSN 0020-1693. Available under: doi: 10.1016/S0020-1693(98)00065-6

Zusammenfassung

The biphenyl-bridged, chiral zirconocene complex rac-2,2'-biphenyl-bis(3,4-dimethylcyclopentadienyl)zirconium dichloride catalyzes the reaction of 1,6- and 1,7-dienes with excess dibutyl magnesium to bis(butyl-magnesio-methyl)-substituted cycloalkane derivatives. Analogous reactions occur with butyl magnesium chloride and with heteroatom-containing dienes. The preference of 1,6-dienes for trans-fused cyclization products and that of 1,7-dienes for cis-fusion at ambient and for trans-fusion at elevated temperatures is similar to that observed before for unsubstituted zirconocene complexes. The R-enantiomer of the biphenyl-bridged zirconocene complex gives trans-fused cyclization products with an optical purity of only 15 ± 1% ee. The stereochemistry of these cyclomagnesation reactions is explained in terms of the relative rates of mutually competing cyclization and transmetalation steps.

Fachgebiet (DDC)

540 Chemie

Schlagwörter

Ansa-zirconocene, catalysis, diene cyclomagnesation

Zitieren

ISO 690

MARTÍN, Sandra, Hans-Herbert BRINTZINGER, 1998. Cyclomagnesation of dienes catalyzed by a chiral ansa-zirconocene. In: Inorganica Chimica Acta. 1998, 280(1-2), pp. 189-192. ISSN 0020-1693. Available under: doi: 10.1016/S0020-1693(98)00065-6

BibTex

@article{Martin1998Cyclo-23885,
  year={1998},
  doi={10.1016/S0020-1693(98)00065-6},
  title={Cyclomagnesation of dienes catalyzed by a chiral ansa-zirconocene},
  number={1-2},
  volume={280},
  issn={0020-1693},
  journal={Inorganica Chimica Acta},
  pages={189--192},
  author={Martín, Sandra and Brintzinger, Hans-Herbert}
}

RDF

<rdf:RDF
    xmlns:dcterms="http://purl.org/dc/terms/"
    xmlns:dc="http://purl.org/dc/elements/1.1/"
    xmlns:rdf="http://www.w3.org/1999/02/22-rdf-syntax-ns#"
    xmlns:bibo="http://purl.org/ontology/bibo/"
    xmlns:dspace="http://digital-repositories.org/ontologies/dspace/0.1.0#"
    xmlns:foaf="http://xmlns.com/foaf/0.1/"
    xmlns:void="http://rdfs.org/ns/void#"
    xmlns:xsd="http://www.w3.org/2001/XMLSchema#" > 
  <rdf:Description rdf:about="https://kops.uni-konstanz.de/server/rdf/resource/123456789/23885">
    <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2013-07-04T07:59:12Z</dc:date>
    <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2013-07-04T07:59:12Z</dcterms:available>
    <dcterms:hasPart rdf:resource="https://kops.uni-konstanz.de/bitstream/123456789/23885/1/Martin_238852.pdf"/>
    <bibo:uri rdf:resource="http://kops.uni-konstanz.de/handle/123456789/23885"/>
    <dcterms:title>Cyclomagnesation of dienes catalyzed by a chiral ansa-zirconocene</dcterms:title>
    <void:sparqlEndpoint rdf:resource="http://localhost/fuseki/dspace/sparql"/>
    <dc:rights>terms-of-use</dc:rights>
    <dcterms:bibliographicCitation>Inorganica Chimica Acta ; 280 (1998), 1-2. - S. 189-192</dcterms:bibliographicCitation>
    <dcterms:rights rdf:resource="https://rightsstatements.org/page/InC/1.0/"/>
    <dc:creator>Brintzinger, Hans-Herbert</dc:creator>
    <dc:contributor>Martín, Sandra</dc:contributor>
    <dcterms:issued>1998</dcterms:issued>
    <dspace:isPartOfCollection rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <dc:language>eng</dc:language>
    <dcterms:isPartOf rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <foaf:homepage rdf:resource="http://localhost:8080/"/>
    <dspace:hasBitstream rdf:resource="https://kops.uni-konstanz.de/bitstream/123456789/23885/1/Martin_238852.pdf"/>
    <dc:creator>Martín, Sandra</dc:creator>
    <dc:contributor>Brintzinger, Hans-Herbert</dc:contributor>
    <dcterms:abstract xml:lang="eng">The biphenyl-bridged, chiral zirconocene complex rac-2,2'-biphenyl-bis(3,4-dimethylcyclopentadienyl)zirconium dichloride catalyzes the reaction of 1,6- and 1,7-dienes with excess dibutyl magnesium to bis(butyl-magnesio-methyl)-substituted cycloalkane derivatives. Analogous reactions occur with butyl magnesium chloride and with heteroatom-containing dienes. The preference of 1,6-dienes for trans-fused cyclization products and that of 1,7-dienes for cis-fusion at ambient and for trans-fusion at elevated temperatures is similar to that observed before for unsubstituted zirconocene complexes. The R-enantiomer of the biphenyl-bridged zirconocene complex gives trans-fused cyclization products with an optical purity of only 15 ± 1% ee. The stereochemistry of these cyclomagnesation reactions is explained in terms of the relative rates of mutually competing cyclization and transmetalation steps.</dcterms:abstract>
  </rdf:Description>
</rdf:RDF>