Facile Construction of Optically Active 1,3-Diols. Synthesis of (2S,4R)-7-Octene-2,4-diol and endo-(1S,3S,5R)- and exo-(1R,3S,5S)-1,3-Dimethyl-2,9-dioxabicyclo[3.3.1]nonane

A short and stereoselective asymmetric synthesis of (2S,4R)-7-octene-2,4-diol (a key intermediate in the Bartlett synthesis of nonactic acid) and two stereoisomers of a biologically active substance isolated from Norway spruce infested by ambrosia beetle, endo-(1S,3S,5R)- and exo-(1R,3S,5S)-1,3-dimethyl-2,9-dioxabicyclo-[3.3.1]nonane, was effectively accomplished in three and four reaction steps, respectively, by starting with easily obtainable (S)-1-(1,3-dithian-2-yl)-2-propanol by baker’s yeast asymmetric reduction. The main strategy was based on a facile construction of optically active β-hydroxy ketones via alkylation of the dianion of (S)-1-(1,3-dithian-2-yl)-2-propanol with alkyl halides, followed by their stereoselective reductions.