Type of Publication: | Journal article |
URI (citable link): | http://nbn-resolving.de/urn:nbn:de:bsz:352-238852 |
Author: | Martín, Sandra; Brintzinger, Hans-Herbert |
Year of publication: | 1998 |
Published in: | Inorganica Chimica Acta ; 280 (1998), 1-2. - pp. 189-192. - ISSN 0020-1693 |
DOI (citable link): | https://dx.doi.org/10.1016/S0020-1693(98)00065-6 |
Summary: |
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.
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Subject (DDC): | 540 Chemistry |
Keywords: | Ansa-zirconocene, catalysis, diene cyclomagnesation |
Link to License: | In Copyright |
MARTÍN, Sandra, Hans-Herbert BRINTZINGER, 1998. Cyclomagnesation of dienes catalyzed by a chiral ansa-zirconocene. In: Inorganica Chimica Acta. 280(1-2), pp. 189-192. ISSN 0020-1693. Available under: doi: 10.1016/S0020-1693(98)00065-6
@article{Martin1998Cyclo-23885, title={Cyclomagnesation of dienes catalyzed by a chiral ansa-zirconocene}, year={1998}, doi={10.1016/S0020-1693(98)00065-6}, number={1-2}, volume={280}, issn={0020-1693}, journal={Inorganica Chimica Acta}, pages={189--192}, author={Martín, Sandra and Brintzinger, Hans-Herbert} }
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