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Christina M White Intramolecular Using this alternative palladium(II) source having a counterion that is a much weaker base, 1H NMR analysis at the same 2 h time point revealed predominant formation of a ð-allylPd complex (ca. 61%) and no significant formation of product 3a. The addition of an external acetate source to this ð-allylPd intermediateled to the formation of 3a with a similar yield and identicaldiastereoselectivity to that observed under standard catalytic conditions. Yields decrease over time，which was most likely due to formation of Pd-H in the oxidative aminopalladation pathway that mediates olefin isomerization to 2a J. AM. CHEM. SOC. 2007, 129, 7274 J. AM. CHEM. SOC. 2008, 130, 3316
Intermaolecular Lewis acid activition Stoichiometric Studies To Evaluate the Role of (salen)CrCl2 The combination of Cr catalyst 2 with BQ was uniquely effective at promoting formation of aminated product 7 in 25% yield with regio- and stereoselectivities similar to those observed under standard catalytic conditions. Consistent with 2/BQ working together to promote functionalization,sterically hindered quinones such as 2,6-dimethyl quinone result in significantly diminished yieldsThese results suggest that Pd catalyst 1 mediates allylic C-H cleavage, while Cr catalyst 2 and BQ promote functionalization. J. AM. CHEM. SOC. 2008, 130, 3316
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Theaminopalladation/-hydride elimination mechanism predicts formation of 22a-d2 but not 22b-d2. The observed formation of nearly equal amounts of products 22a-d2 and 22b-d2, however, argued against the possibility of aminopalladation/-hydride elimination pathway and in favor of a mechanism involving aπ-allyl-Pd intermediate. Org. Lett., 2009, 11, 2707 J. AM. CHEM. SOC. 2010, 132, 11978
Conclusions: 1. All Pd(0)-catalyzed allylic aminations was promoted by chiral phosphines can not avoid regioselectivity directly. No other kinds of chiral organomoleculars was used. Most of them need additives and excess substrates(3 eq. of amines or even more) to prevent bypath product. 2. Most of Pd(ll)-catalyzed allylic aminations need additives to obtain product and high regioselectivity. Substrates were limited to functionalized amines.Consice mechanisms needed to be studied.