Synthesis of α-Acyloxyketone Derivatives via the Platinum-Catalyzed Migration of Propargylic Esters.
The synthesis of α-acyloxyketones via the migration of a propargylic ester followed by the intramolecular nucleophilic addition of the resulting allene was achieved using a cationic platinum catalyst. The optimized conditions for this transformation were determined to be 3 mol% of Pt(cod)Cl2, 3 mol% of AgNTf2, and 3 eq of water in toluene at 100 °C, and these conditions were successfully applied to the synthesis of a wide variety of α-aryl-α-acyloxyketones. The mechanism of this reaction was evaluated in detail based on the results of isotope labeling experiments using H2(18)O.
Graduate School of Pharmaceutical Sciences, Kyoto University.
Chihiro
C
Tsukano
Sho
S
Yamamoto
Yoshiji
Y
Takemoto
D000096:Acetone / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D000480:Alkynes / Q000737:chemistry*; D002384:Catalysis; D004952:Esters / Q000737:chemistry*; D004987:Ethers / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D009944:Organoplatinum Compounds / Q000737:chemistry*; D010984:Platinum / Q000737:chemistry*
D000480:Alkynes; D004952:Esters; D004987:Ethers; D009944:Organoplatinum Compounds; D000096:Acetone; D010984:Platinum