Regioselective enzymatic undecylenoylation of 8-chloroadenosine and its analogs with biomass-based 2-methyltetrahydrofuran as solvent

2-Methyltetrahydrofuran (MeTHF), a biomass-derived compound, is a promising medium for biocatalysis and organometallic reactions. The regioselective acylation of 8-chloroadenosine (8-Cl-Ado) and its analogs was carried out in MeTHF with immobilized Penicillium expansum lipase. The lipase displayed more than twofold higher catalytic activity and much better thermostability in MeTHF than in other organic solvents and co-solvent systems. The optimum reaction medium, enzyme dosage, molar ratio of viny ester to nucleoside and reaction temperature for the enzymatic acylation of 8-Cl-Ado were MeTHF, 25 U/mL, 7.5 and 35 degrees C, respectively, under which the desirable 5'-O-undecylenoyl-8-Cl-Ado was obtained with a yield of 95% and a regioselectivity of >99% in 3 h. In addition, the lipase catalyzed regioselective undecylenoylation of other purine nucleosides, producing 5'-undecylenic acid esters with moderate to high yields (63-94%) and excellent 5'-regioselectivities (94->99%). Use of biomass-derived solvents might open up novel opportunities for sustainable and greener biocatalytic processes. (C) 2012 Elsevier Ltd. All rights reserved.