The reaction of different allylic chloromethyl ethers with an excess of lithium powder (1: 7 molar ratio) and a catalytic amount of DTBB (2.5 mol%) in THF at 0° C for 1h gives, after hydrolysis with water, the expected alcohols resulting from a [2, 3]-Wittig rearrangement, in an exclusive manner. The same process can also be applied to the corresponding [1, 2]- Wittig rearrangement, as it is exemplified for benzyl chloromethyl ether.
