Palladium-Catalyzed Carbo-Oxygenation of Propargylic Amines using in Situ Tether Formation
Phillip D G Greenwood1, Erwann Grenet1, Jerome Waser1
1Laboratory of Catalysis and Organic Synthesis, EPFL SB ISIC LCSO, BCH 4306, Ecole Polytechnique Fédérale de Lausanne, 1015, Lausanne, Switzerland.
Abstract:
1,2-Amino alcohols and α-aminocarbonyls are frequently found in natural products, drugs, chiral auxiliaries, and catalysts. This work reports a new method for the palladium-catalyzed oxyalkynylation and oxyarylation of propargylic amines. The reaction is perfectly regioselective based on the in situ introduction of a hemiacetal tether derived from trifluoroacetaldehyde. cis-Selective carbo-oxygenation was achieved for terminal alkynes, whereas internal alkynes gave trans-carbo-oxygenation products. The obtained enol ethers could be easily transformed into 1,2-amino alcohols or α-amino ketones using hydrogenation or hydrolysis, respectively.
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