[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-butyl-biphenyl (2.5 mol %) in THF at 0 degrees C leads to the corresponding alpha-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. (c) 2006 Elsevier Ltd. All rights reserved.