Selective isomerization of 1,2-epoxyalkanes to aldehydes with lithium dialkylamides

Reaction of a variety of 1,2-epoxyalkanes with 2.5 equiv. of bulky metal amide—lithium 2,2,6,6-tetramethylpiperidide—affords the corresponding aldehydes exclusively in high yields; this is the first example of base-promoted isomerization of monosubstituted epoxides to aldehydes.