Rhodium-catalyzed methylthio transfer reaction between ketone alpha-positions: reversible single-bond metathesis of C-S and C-H bonds.
In the presence of a catalytic amount of RhH(PPh(3))(4) and 1,2-bis(diphenylposphino)ethane (dppe), alpha-phenylthio ketones were methylthiolated with p-cyano-alpha-methylthioacetophenone giving alpha-phenylthio-alpha-methylthio ketones. The methylthio transfer reaction between the ketone alpha-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.
Arisawa
Mieko
M
Department of Organic Chemistry, Graduate School of Pharmaceutical Sciences, Tohoku University, Sendai 980-8578, Japan.
Suwa
Katsunori
K
Yamaguchi
Masahiko
M
D002384:Catalysis; D005459:Fluorides / Q000138:chemical synthesis / Q000737:chemistry*; D007659:Ketones / Q000138:chemical synthesis / Q000737:chemistry*; D008698:Mesylates / Q000737:chemistry; D015394:Molecular Structure; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism; D013457:Sulfur Compounds / Q000138:chemical synthesis / Q000737:chemistry*
D007659:Ketones; D008698:Mesylates; D013457:Sulfur Compounds; C523090:sulfur fluoride; D012238:Rhodium; D005459:Fluorides