[1,2]-Wittig rearrangement from chloromethyl ethers

The reaction of different chloromethyl ethers 1 with an excess of lithium powder and a catalytic amount of 4,4′-di-tert-butylbiphenyl (2.5 mol %) in THF at 0 °C leads to the corresponding α-lithiomethyl ether intermediates, through a chlorine-lithium exchange, which spontaneously undergo a clean 1,2]-Wittig rearrangement affording the expected homobenzylic alcohols 2. This is the first version of this rearrangement starting from easily available chloromethyl ethers.