Oxyfunctionalization of Allyl Thioether Ruthenium Complexes with Dimethyldioxirane

Abstract Allyl thioether complexes [CpRu(P-P)(SRR′)]PF₆ (P-P = Ph₂PCH₂PPh₂ (dppm), Ph₂PC₂H₄PP₂ (dppe), R = Me, Et, Ph, R′ = 3-propenyl, 3-cyclohexenyl, 2-methyl-2-buten-4-yl) and [CpRu(chir)(SRR′)]PF₆ (chir = (S,S)-Ph₂PCHMeCHMePPh₂, R = Me, CH₂Ph, R′ = 2-methyl-2-buten-4-yl) are obtained from the corresponding thiolate complexes by reaction with the appropriate allyl bromide. Careful oxidation with dimethyldioxirane (DMD) gave the allyl sulfoxide complexes [CpRu(P-P)(MeS(O)CH₂CH=CH₂)]PF₆ (P-P = dppm, dppe). Double oxidation to the corresponding sulfinylmethyl epoxide complexes can be readily achieved with an excess of DMD. Oxidation of the chir complexes proceeds with only moderate diastereoselectivity. The structure of the (R, R/S, S) diastereomer of [CpRu(dppm)(MeS(O)CH₂CHCH₂O)]PF₆ was determined: monoclinic space group P2₁/c (No. 14), a = 11.21(2), b = 16.762(9), c = 18.45(4) Å, β = 94.4(1)°, Z = 4. For a representative example, the decomplexation of the sulfoxide-epoxide ligand by sodium iodide in acetone was demonstrated.