Five optically active acyloins were prepared by Sharpless dihydroxylation of silyl enol ethers as intermediates starting from the corresponding ketones. 4-heptanone, 5-nonanone, 2,6-dimethyl-4-heptanone, 5-Methyl-3-hexanone and 4-Phenyl-2-butanone reacted with Me3SiCl or Me3SiI under the presence of different bases to give a kinetically controlled or thermally stable silyl enol ether. The obtained silyl enol ethers were oxidized through Sharpless asymmetric dihydroxylation using AD-mix- or  to give (S)-acyloins in >62% ee or (R)-acyloins in >75% ee respectively except the silyl enol ether derived from 5-methyl-3-hexanone. This silyl enol ether were oxidized to give (R)-acyloin whether AD-mix- or  was used. AD-mix- gave a 16% ee while AD-mix- gave a 76% ee. However, the silyl enol ether was oxidized by Oxone and Shi’s catalyst derived from D- or L-fructose to give (R)-acyloin in a 75% ee of (S)-acyloin in a 73% ee respectively.