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An intermolecular C(sp3)H amination using a Pd0/PAr3 catalyst was developed. The reaction begins with oxidative addition of R2NOBz to a Pd0/PAr3 catalyst and subsequent cleavage of a C(sp3)H bond by the generated PdNR2 intermediate. The catalytic cycle proceeds without the need for external oxidants in a similar manner to the extensively studied palladium(0)‐catalyzed CH arylation reactions....
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