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DOI: 10.1055/s-2005-862384
A Comment on the Gurjar Mechanism for Alkene Isomerization Using the Grubbs Olefin Metathesis Catalysts
Publication History
Publication Date:
22 February 2005 (online)
Abstract
The mechanism of allylic alcohol isomerization in the presence of the Grubbs metathesis catalysts is discussed.
Key words
Grubbs - atom transfer - isomerization - mechanism - allylic alcohol - metathesis
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8c To our knowledge there are no reports of β-hydride elimination reactions in the sense depicted by Gurjar (i.e. exocyclic to the metallacycle) in Scheme 2. However, endocyclic β-alkyl, β-hydride and β-silyl elimination reactions of ruthenacyclobutanes have been documented or inferred. β-H eliminations in related iridium complexes also proceed via cleavage of an endocyclic C-H bond. See:
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We have yet to rule out the possibility that this ‘isomerization’ reaction might proceed via an elimination-intermolecular Kharasch sequence. Experiments are in hand to differentiate between these alternate pathways.
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in this study Grubbs reported the 1,2-addition of hydride (rather than conjugate reduction) to an α,β-unsaturated ketone when treated to propan-2-ol, H2 and NaOH in the presence of post-metathesis catalyst.
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20a Prepared by the addition of vinyl magnesium bromide to benzaldehyde-1-d
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