Practical generation of 3,5‐dimethoxybenzyllithium: application to the synthesis of 5‐substituted‐resorcinols

Reductive lithiation of 3,5‐dimethoxybenzyl methyl ether was successfully performed with lithium wire and a catalytic amount of naphthalene in dry tetrahydrofuran at −15°C, leading to the quantitative generation of 3,5‐dimethoxybenzyllithium. This organometallic compound, which can be stored for at least 24 h, was trapped with a variety of different electrophiles, including, besides aldehydes, non‐functionalized and functionalized alkyl halides and an epoxide. Accordingly, it is a useful intermediate in the synthesis of 5‐substituted natural and non‐natural resorcinols. Copyright © 2003 John Wiley & Sons, Ltd.