(Chemical Equation Presented) In the presence of a catalytic amount of RhH(PPh3)4 and 1,2-bis(diphenylposphino)ethane (dppe), α-phenylthio ketones were methylthiolated with ρ-cyano-α- methylthioacetophenone giving α-phenylthio-α-methylthio ketones. The methylthio transfer reaction between the ketone α-positions was reversible and at equilibrium, and the methylthio group was transferred in preference to the phenylthio group. The reaction of tertiary alkyl methylthiomethyl ketones proceeded in high yields; the reaction of diastereomeric 4-(tert-butyl)-2-phenylthiocyclohexanones gave an axial 2-methylthiolated product.
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