An efficient regiocontrolled synthesis of substituted and annulated 1,
4-dimethoxynaphthalenes as precursors for 1,4-naphthoquinone systems h
as been developed through naphthoannulation route by regioselective 1,
2-addition of 2,5-dimethoxybenzylmagnesium chloride to acyclic and cyc
lic alpha-oxoketene dithioacetals and subsequent BF3. OEt2 assisted cy
cloaromatization of the resulting alcohols.