Base-Mediated Cascade Rearrangements of Aryl-Substituted Diallyl Ethers
Reid, Jolene P
McAdam, Catherine A
Johnston, Adam JS
Cook, Matthew J
The Journal of Organic Chemistry
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Reid, J. P., McAdam, C. A., Johnston, A. J., Grayson, M., Goodman, J., & Cook, M. J. (2014). Base-Mediated Cascade Rearrangements of Aryl-Substituted Diallyl Ethers. The Journal of Organic Chemistry, 80 1472-1498. https://doi.org/10.1021/jo502403n
Two base mediated cascade rearrangement reactions of diallyl ethers were developed leading to selective [2,3]-Wittig-oxy-Cope and isomerization-Claisen rearrangements. Both diaryl and aryl-silyl substituted 1,3-substituted propenyl substrates were examined and each exhibits unique reactivity and different reaction pathways. Detailed mechanistic and computational analysis was conducted which demonstrated that the role of the base and solvent were key to the reactivity and selectivity observed. Crossover experiments also suggest that these reactions proceed with a certain degree of dissociation and the mechanistic pathway is highly complex with multiple competing routes.
We thank Eli Lilly (Dr Magnus Walter and Dr Maria Whatton) for a CASE award to C.A.M. and Queen’s University Belfast for funding. We also thank Girton College, Cambridge (Research Fellowship to M.N.G.) and Unilever for support.
External DOI: https://doi.org/10.1021/jo502403n
This record's URL: https://www.repository.cam.ac.uk/handle/1810/246942