Rhodium-Catalyzed Acyl-Transfer Reaction between Benzyl Ketones and Thioesters: Synthesis of Unsymmetric Ketones by Ketone CO–C Bond Cleavage and Intermolecular Rearrangement

• Published in: Organic letters Vol. 14; no. 14; pp. 3804 - 3807
• Main Authors: Arisawa, Mieko, Kuwajima, Manabu, Toriyama, Fumihiko, Li, Guangzhe, Yamaguchi, Masahiko
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 20.07.2012; Amer Chemical Soc
• Subjects: Benzene Derivatives - chemical synthesis; Benzene Derivatives - chemistry; Catalysis; Chemistry; Chemistry, Organic; Esters; Ketones - chemical synthesis; Ketones - chemistry; Molecular Structure; Nitriles - chemical synthesis; Nitriles - chemistry; Organophosphonates - chemical synthesis; Organophosphonates - chemistry; Physical Sciences; Propane - analogs & derivatives; Propane - chemical synthesis; Propane - chemistry; Rhodium - chemistry; Science & Technology; Stereoisomerism; ACYLATION REACTION; CHLORIDES; ACTIVATION; CARBON-CARBON BONDS; REAGENTS
• ISSN: 1523-7060; 1523-7052
• DOI: 10.1021/ol3017148

In the presence of catalytic amounts of RhH(CO)(PPh3)3 and 1,2-bis(diphenylphosphino)benzene (dppBz), acyl groups were transferred between benzyl ketones and thioesters/aryl esters. The rhodium complex catalyzed the cleavage of ketone CO–C bonds and intermolecular rearrangement giving unsymmetric ketones. The acyl-transfer reaction also occurred with 1-(p-chlorophenyl)-3-(p-cyanophenyl)propane-2-one giving unsymmetric ketones.