Rhodium-Catalyzed Methylthio Transfer Reaction between Ketone α-Positions: Reversible Single-Bond Metathesis of C−S and C−H Bonds

In the presence of a catalytic amount of RhH(PPh<sub>3</sub>)<sub>4</sub> and 1,2-bis(diphenylposphino)ethane (dppe), α-phenylthio ketones were methylthiolated with <i>p</i>-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-(<i>tert</i>-butyl)-2-phenylthiocyclohexanones gave an axial 2-methylthiolated product.