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The mere presence or absence of PPh3 suffices to control the reactivity of bis(η3-allyl)palladium complexes. In the absence of PPh3 they undergo chemoselective allylic addition to aldehydes or imines, even in the presence of allylic chlorides, whereas in the presence of PPh3 the Stille coupling reaction takes place chemoselectively, even when aldehydes or imines are also present (see scheme).
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Nakamura et al. (2001) studied this question.
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