| Abstract: | Low-temperature lithium–iodine exchange between tert-butyllithium and the appropriate iodide has been used to generate 3-oxa-5-hexenyllithium and a variety of 4-oxa-5-hexenyllithiums. The 3-oxa system is inherently unstable and fragments via facile β-elimination to give the anion of allyl alcohol and ethylene. The 4-oxa-5-hexenyllithiums, in contrast, are stable at low temperatures but undergo novel isomerization upon warming to deliver the lithium salt of a 4-alken-1-ol in the formal equivalent of an unprecedented [1,4]-Wittig rearrangement. The rearrangement is most likely mediated by 5-exo-trig ring closure of the 4-oxa-5-hexenyllithium to a (2-tetrahydrofuranyl)methyllithium followed by rapid opening to the alkoxide. |
