Rhodium-catalyzed acyl-transfer reaction between benzyl ketones and thioesters: synthesis of unsymmetric ketones by ketone CO-C bond cleavage and intermolecular rearrangement.
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.
Department of Organic Chemistry, Graduate School of Pharmaceutical Sciences, Tohoku University , Aoba, Sendai 980-8578, Japan.
Mieko
M
Arisawa
Manabu
M
Kuwajima
Fumihiko
F
Toriyama
Guangzhe
G
Li
Masahiko
M
Yamaguchi
D001555:Benzene Derivatives / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D004952:Esters; D007659:Ketones / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D009570:Nitriles / Q000138:chemical synthesis* / Q000737:chemistry; D063065:Organophosphonates / Q000138:chemical synthesis* / Q000737:chemistry; D011407:Propane / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism
C519449:1,2-bis(diphenylphosphino)benzene; C588312:1-(p-chlorophenyl)-3-(p-cyanophenyl)propane-2-one; D001555:Benzene Derivatives; D004952:Esters; D007659:Ketones; D009570:Nitriles; D063065:Organophosphonates; D012238:Rhodium; D011407:Propane