Base-mediated cascade rearrangements of aryl-substituted diallyl ethers.
Type
Article
Change log
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.
Description
Keywords
Catalysis, Ethers, Isomerism, Molecular Structure, Propane, Silanes
Journal Title
J Org Chem
Conference Name
Journal ISSN
0022-3263
1520-6904
1520-6904
Volume Title
80
Publisher
American Chemical Society (ACS)
Publisher DOI
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.