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Cyclooctanoid ring systems from mixed acetals via heteroatom-assisted [1,2]-shift of oxonium ylides
Fredrik P Marmsäter1, Graham K Murphy, F G West
1Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada T6G 2G2.
Abstract:
Cyclic mixed acetals with pendant diazoketone side chains undergo efficient rearrangement to ether-bridged cyclooctanoid systems upon treatment with Cu(hfacac)2. This result demonstrates that heterosubstituted carbons are suitable migrating groups for the Stevens [1,2]-shift of oxonium ylides. In the case of a mixed thioacetal, the resulting sulfide served as a trigger for cleavage of the bridging ether through one of two complementary strategies, furnishing a bicyclo[6.3.0]octene product with an angular hydroxyl group.
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