Abstract: The structural unit of 2-alkylidene-5-hydroxymethyltetrahydrofunan exists in some natural compounds such as the macrotetrolide antibiotics and the ocean natural products Sarcodictyin and Eleutherobin. These natural compounds usually show outstanding biological activities. In this work we decribed a totally new method for the constructing of this structural unit by employing indirect electrolysis, namely, using KI and NaI as the indirect electrolyte, water as solvent and reagent, the γ-alkylation products of β-Ketoesters as the starting material. Thirteen kinds of 2-alkylidene-5-hydroxymethyltetrahydrofunans were synthesized in high yields and good selectivity. The success of this method has not only provided a “clean technology” of indirect electrolysis but also prompted a simple, effective and environmental friendly green synthesis.

Key words: 2-Alkylidene-5-hydroxymethyltetrahydrofunans, β-Ketoester, Electrochemical synthesis, Green synthesis