Scope and limitations of the catalytic asymmetric rearrangement of epoxides to allylic alcohols using chiral lithium amide bases/lithiated imidazoles |
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Authors: | Sally J Oxenford Peter O’Brien Narendra Panday |
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Institution: | a Department of Chemistry, University of York, Heslington, York YO10 5DD, UK b F. Hoffmann-La Roche Ltd, CH-4070 Basel, Switzerland c GlaxoSmithKline Pharmaceuticals, Medicines Research Centre, Gunnels Wood Road, Stevenage SG1 2NY, UK |
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Abstract: | The catalytic asymmetric rearrangement of functionalised cyclohexene and cyclopentene oxides has been studied using sub-stoichiometric amounts of a chiral lithium amide in combination with a stoichiometric amount of three different lithiated imidazoles. 1-Methylimidazole that had been lithiated at the C-2 aryl position gave the highest enantioselectivity (82% ee). With 1,2-dimethylimidazole that had been lithiated at the C-2 methyl group, epoxide ring opening occurred as an unexpected and competing process. Ultimately, ring opening was suppressed using a more sterically hindered imidazole. In all catalytic examples, a racemic background reaction (presumably due to rearrangement by the lithiated imidazoles) was observed. |
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Keywords: | Epoxides Allylic alcohols Chiral bases Imidazoles |
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