Synthetic and Mechanistic Studies of Strained Heterocycle Opening Reactions Mediated by Zirconium(IV) Imido Complexes
The reactions of the bis(cyclopentadienyl)(tert-butylimido)zirconium complex (Cp(2)Zr=N-t-Bu)(THF) (1) with epoxides, aziridines, and episulfides were investigated. Heterocycles without accessible beta-hydrogens undergo insertion/protonation of the C-X bond to produce 1,2-amino alcohols (X = O) and...
| Veröffentlicht in: | Organometallics. - 1998. - 24(2005), 7 vom: 28. März, Seite 1647-1659 |
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| 1. Verfasser: | |
| Weitere Verfasser: | , , , |
| Format: | Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2005
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| Zugriff auf das übergeordnete Werk: | Organometallics |
| Schlagworte: | Journal Article |
| Zusammenfassung: | The reactions of the bis(cyclopentadienyl)(tert-butylimido)zirconium complex (Cp(2)Zr=N-t-Bu)(THF) (1) with epoxides, aziridines, and episulfides were investigated. Heterocycles without accessible beta-hydrogens undergo insertion/protonation of the C-X bond to produce 1,2-amino alcohols (X = O) and 1,2-diamines (X = NR), whereas heterocycles with accessible beta-hydrogens undergo elimination/protonation to produce allylic alcohols (X = O) and allylic sulfides (X = S). Mechanistic investigations support a stepwise pathway with zwitterionic intermediates for the first reaction class and a concerted pathway for the second reaction class. Additionally, the feasibility of chirality transfer from the planar-chiral ebthi (ebthi = ethylenebis(tetrahydroindenyl)) ligand was demonstrated with a chiral analogue, (ebthi)-Zr=NAr(THF) (Ar = 2,6-dimethylphenyl), 2, through the diastereoselective ring opening of meso epoxides |
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| Beschreibung: | Date Revised 29.09.2020 published: Print Citation Status PubMed-not-MEDLINE |
| ISSN: | 0276-7333 |