Lipase catalyzed kinetic resolution of racemic cis-6-( tert-butyldimethylsilyloxy)-3,6-dihydro-2 H-pyran-3-ol ( rac)- 1 was achieved in high enantiomeric excess. Transesterification of ( rac)- 1 with vinylacetate in t BuOMe yielded the alcohol (3 S,6 R)- 1 in 99.0% ee, whereas (3 R,6 S)- 1 was obtained, in 99.0% ee, by the lipase catalyzed ester hydrolysis of acetate (3 R,6 S)- 2, which was obtained along with the transesterification. Both (3 S,6 R)- 1 and (3 R,6 S)- 1 were subjected to oxidation to provide the corresponding 6-silyloxy-3-pyranone (6 R)- 3 and (6 S)- 3, respectively. Application to the synthesis of 7, which is the key intermediate of asymmetric synthesis of pseudomonic acid A 9 is also described.