Silaboration of 1,3-cyclohexadiene in the presence of Pt(acac) 2 , DIBALH, and a phosphoramidite prepared from (S)-1,1'-bi-2-naphthol and diisopropylamine led to (1R,4S)-1-(dimethylphenylsilyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-cyclohexene with 70% ee. Chiral catalysts based on Ni gave no or essentially racemic product, whereas complexes containing Pd were inactive.