1,4-Dioxaspiropentanes. Synthesis, Spectroscopic Properties, and Reactions with Nucleophiles

Article abstract of DOI:10.1021/jo00003a044

A number of simple allenes have been converted cleanly to the corresponding 1,4-dioxaspiro<2.2>pentanes in good yields by oxidation with dimethyldioxirane.Mono- and trisubstituted allenes give the anti diastereomers with good stereoselectivity, whereas 1,3-disubstituted allenes show only a slight preference for the anti,anti isomers, unless steric effects are extreme.Stereochemical assignments are based on steric considerations and a consistent set of NMR characteristics that permit structural attributions.The addition of a range of nucleophiles (water, alcohols, amines, thiophenol, acetate, chloride, and fluoride) to these intermediates proceeded smoothly under buffered conditions to give highly functionalized products of general type 5.These reactions were shown to take place with the appropriate selectivities for S_N2 substitutions in instances where these features were observable, namely, regioselective attack at the less-substituted epoxide carbon and inversion of configuration at the site of substitution.Under acid conditions dioxaspiropentanes gave mixtures of other types of products, which appear to arise from carbocationic processes.