A mechanistically unusual base induced [1,3]-H-shift in homoallylic ethers

Article abstract of DOI:10.1016/S0040-4039(97)01223-9

Upon treatment with NaH in DMF the homoallylic ethers 1a-g and the amine 1h undergo a rearrangement into the trisubstituted (E)-olefins 2a-h. Experiments with isotopically labelled forms of 1a and 1b show that the [1,3]-shift is cleanly intramolecular and proceeds predominantly in the suprafacial mode.