Short Regioselective Chemoenzymatic Synthesis and Biological Evaluation of 1OAcyl2OβDsulfoquinovopyranosylsnglycerols

A convenient chemoenzymatic synthesis of a new class of nonnatural sulfoglycolipids – 2OβDsulfoquinovosylmonoacylglycerols 2OβDSQMG – derived from 2OβDglucopyranosylglycerol and carrying acyl chains ofvarious lengths at the 1position of the snglycerol moiety, was performed with the aid of a key step involving regioselective lipasecatalyzed acylation of 2O6deoxy6tosylβDglucopyranosylsnglycerol 4 at its 1position, reported here for the first time. Elaboration of the sugar moiety through thioacetate substitution of the selectively inserted tosyl group with subsequent Oxone®oxidation in the presence of unprotected primary and secondary hydroxy groups efficiently afforded the target compounds, the hexanoyl, dodecanoyl, and octadecanoyl derivatives 1a–c, which were active when tested in the EBVEA in vitro assay for antitumor promoters. © WileyVCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009