Oxyamination and 1,4-chloroamination

In these reactions, the nitrogen nudeophile is typically an amide, carbamate, or a sulfonamide. Because of the low nudeophiUdty of such nitrogen functions, no intermolecular 1,4-addition involving C-N bond formation is known. In aU cases reported, the carbon-nitrogen coupling takes place in an intramolecular aminopalladation. 

Depending on the reaction conditions, it was possible to achieve trans- or ds-1,4-oxyamination by choice. As with the other Pd(11)-catalyzed 1,4-additions, Cl (from LiCl) is used as a steering ligand to control the stereochemistry. When the chloride concentration is increased, a cis-l,4-chloroamination takes place. 

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Intramolecular 1,4-Oxyamination and 1,4-Chloroamination Palladium-catalyzed oxidation of dienylcarboxamides 107 in acetone in the presence of acetic acid gives oxyamination products by stereoselective reactions (Scheme 11.39) [128]. 

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