diethoxymethyltributyltin affords a large variety of new α-stannylacetals, which are expected to have a high potential for selective organic synthesis when they contain labile or chiral alkoxy groups. The α-stannylacetals can be converted into the corresponding substituted α-stannyl-ethers by treatment with organoaluminium halides or by use of an acetyl chloride/Grignardreagent sequence. The study has concentrated