Chemo-Enzymatic Synthesis of 13-S-Hydroxyoctadecadienoic Acid (13-S-HODE)

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Abstract
A new method of preparation of optically active 13-S-hydroxyoctadecadienoic acid (13-HODE) is described. The key chemical step involves the coupling of methyl Z-10-iododec-9-enoate and tri-n-butyl(3(S)-dimethyl-tert-butylsilyloxy)-oct-l-enylstannane using a palladium (II) catalyst. The stannane is readily prepared from 3(S)-oct-l-yn-3-ol and various methods of producing this optically active material are described. In particular the enantioselective hydrolysis of (±)-3-acyloxyoct-l-ynes using an isolated enzyme is reported and this work is compared with results obtained using a whole cell system. Using the lipase from Mucor miehei a small advantage (in terms of the rate of the hydrolysis and the enantioselectivity of the process) is gained by using a chloroalkanoate instead of the corresponding ester possessing an isosteric methyl group in place of the halogen atom. However the best method for kinetic resolution of a racemic 3-acyloxyoct-l-yne involves the use of bakers' yeast (Glänzer, 1987). The new synthesis of 13-S-HODE compares favourably with pre-existing routes in terms of efficiency and overall yield.