Aldol reaction of the amine free Li enolate of tetrahydro-4H-thiopyran-4-one with 1, 4-dioxa- 8-thiaspiro [4.5] decane-6-carboxaldehyde gives mainly the 2, 3-anti-3, 4-syn aldol (7: 1) in good yield; reaction of the LDA generated lithium enolate proceeds poorly. Using the trimethylsilyl enol ether and TiCl4 gives the 2, 3-syn-3, 4-syn aldol (> 10: 1). The adducts can be used for polypropionate synthesis.