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LiCl efficiently catalyzes cyanosilylation of various hetero-substituted ketones. α,α-Dialkoxy ketones are completely converted to silylated cyanohydrins with a substrate-to-catalyst molar ratio of 100,000 at room temperature. Acetophenones substituted by an electron-attracting group at the ortho or para position show higher reactivity than substrates with an electron-donating function.