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Solid-phase Synthesis of [4.4] Spirocyclic Oximes
Published on: February 6, 2019
Stereoselectivity in Oxyallyl-Furan 4+3 Cycloadditions: Control of Intermediate Conformations and Dispersive
Elizabeth H Krenske1, K N Houk, Andrew G Lohse
1Department of Chemistry and Biochemistry, University of California, Los Angeles, CA 90095, USA.
Abstract:
Chiral oxazolidinones were previously thought to control cycloaddition stereoselectivity by steric crowding of one face of the substrate. We have discovered that in 4+3 cycloaddition reactions of oxallyls, the stereoinduction is caused instead by stabilising CH-π interactions that lead to reaction at the more crowded face of the oxazolidinone. Density functional theory calculations on the 4+3 cycloadditions of oxazolidinone-substituted oxyallyls with furans establish unexpected transition state conformations and a new explanation of selectivity.
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