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Base-mediated cascade rearrangements of aryl-substituted diallyl ethers.


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Authors

Reid, Jolene P 
McAdam, Catherine A 
Johnston, Adam JS 
Grayson, Matthew N 
Goodman, Jonathan M 

Abstract

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 arylsilyl-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 was 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.

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Keywords

Catalysis, Ethers, Isomerism, Molecular Structure, Propane, Silanes

Journal Title

J Org Chem

Conference Name

Journal ISSN

0022-3263
1520-6904

Volume Title

80

Publisher

American Chemical Society (ACS)
Sponsorship
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.