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[摘要]：Palladium-catalyzed decarboxylative alpha-allylation of nitriles readily occurs with use of Pd-2(dba)(3) and rac-BINAP. This catalyst mixture also allows the highly regiospecific alpha-allylation of nitrites in the presence of much more acidic (x-protons. Thus, the reported method provides access to compounds that are not readily available via base-mediated allylation chemistries. Lastly, mechanistic investigations indicate that there is a competition between C- and N-allylation of an intermediate nitrile-stabilized anion and that N-allylation is followed by a rapid [3,3]-sigmatropic rearrangement. |
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