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 ...
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